Polymer, polymer solution, photosensitive resin composition, and cured product

Abstract

To provide a polymer from which a resin cured product that has improved heat characteristics, thereby is excellent in workability and pattern formability in photolithography processing, and has a good balance among sensitivity, alkali solubility and heat-yellowing resistance can be provided.SOLUTION: A polymer includes at least one structural unit selected from a structural unit including two or more (meth)acryloyl groups, and a structural unit including one (meth)acryloyl group, wherein a softening point of the polymer is 0°C or higher and 100°C or lower.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polymer, a polymer solution containing the polymer, a photosensitive resin composition containing the polymer solution, and a cured product of the photosensitive resin composition.

Background Art

[0002] Liquid crystal display devices and solid-state imaging devices usually include color filters, black matrices, spacers (e.g., photo spacers, colored spacers, black spacers), and partition wall materials (e.g., transparent banks, black banks). The color filter, black matrix, spacer, and partition wall material have a structure in which structures such as colored patterns and protective films are formed on a substrate. Among these structures, as a method for forming a colored pattern or a protective film, a method of forming by photolithography using a photosensitive resin composition has become mainstream. Regarding photosensitive resin compositions, various studies have been made conventionally. For example, in Patent Document 1, an alkali-soluble resin having a group having an acidic group and two or more different polymerizable unsaturated groups at least in a side chain, a polymerizable compound, and a photosensitive resin composition containing a photopolymerization initiator are described. Further, in the examples of Patent Document 1, it is described that a methacrylic acid / methacrylic acid allyl / glycidyl adduct was synthesized as an alkali-soluble resin, and a photosensitive resin composition was prepared using this.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] For a photosensitive resin composition for forming a color filter, a black matrix, a spacer, or a partition member, a resin having a property of undergoing a polymerization reaction by light and curing is used. The color filter, black matrix, spacer, or partition member is produced by patterning the photosensitive resin composition by exposure and development and then curing it. In the photosensitive resin composition, "enhanced sensitivity" seems to be a common issue, but with the complication and spread of display devices and imaging devices, an even higher level of enhanced sensitivity is required. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, and the productivity can be improved. In addition, the photosensitive resin composition is required to have excellent processability in a developing process using an alkaline developer. Furthermore, the cured product of the photosensitive resin composition is required to have high transparency. In addition, particularly when a dye or a pigment is contained in the photosensitive resin composition, light hardly reaches the bottom surface of the pattern compared to the upper surface of the pattern during exposure, and curing by exposure becomes insufficient, and a phenomenon may occur in which the side portion of the bottom surface of the pattern dissolves during development. At that time, if the pattern melts by heat during curing after development, the dissolved portion of the side portion of the bottom surface of the pattern can be filled, so the cured product of the photosensitive resin composition is required to have a low softening point and melting point.

Means for Solving the Problems

[0005] The present inventors have found that by improving the polymer used in the photosensitive resin composition and the formulation of the composition, a resin cured product having a low softening point and melting point, excellent processability and pattern formability in photolithography processing, and a good balance of sensitivity, alkali solubility, and heat resistance yellowing resistance can be obtained, and thus the present invention has been achieved.

[0006] According to the present invention, the following polymers, polymer solutions, photosensitive resin compositions, and cured products are provided. [1] A polymer containing at least one structural unit selected from the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), The softening point of the polymer is 0 °C or higher and 100 °C or lower, [Chemical formula] In formula (1-2), R p is a group having two or more (meth)acryloyl groups, and R 22 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, [Chemical formula] In formula (1-3), R s is a group having one (meth)acryloyl group, and R 22 is a hydrogen atom or an organic group having 1 to 3 carbon atoms. Polymer. The polymer according to item [1] of [2], further comprising at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), the structural unit represented by formula (IN), the structural unit represented by formula (AK), and the structural unit represented by formula (CA), [Chemical formula] In formula (NB), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2, [Chemical formula] In formula (ST), R 40 , R 41 and R 42 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R 43 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, [Chemical formula] In formula (IN), R 61 ~R 68is, independently, a hydrogen atom or an organic group having 1 to 30 carbon atoms, [Chemical formula] In formula (AK), R 71 , R 72 , R 73 and R 74 At least one of them is a linear or branched alkyl group having 3 or more carbon atoms, and the rest of R 71 , R 72 , R 73 and R 74 are, independently, a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, [Chemical formula] In formula (CA), X 51 is a single bond or a linear or branched alkylene group having 1 or more carbon atoms, When X 51 is a single bond, at least one of R 51 , R 52 and R 53 is a linear or branched alkyl group having 2 or more carbon atoms, and the rest of R 51 , R 52 and R 53 are a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, When X 51 is a linear or branched alkyl group having 1 or more carbon atoms, R 51 , R 52 and R 53 are, independently, a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, a polymer. [3] The polymer according to item [2], further includes at least one structural unit selected from the structural unit represented by formula (MI) and the structural unit represented by formula (AD), [Chemical formula] In formula (MI), R31 is a hydrogen atom or an organic group having 1 to 30 carbon atoms, R 32 and R 33 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, [Chemical formula] In formula (AD), R 11 and R 12 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, and R 13 and R 14 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a polymer. [4] The polymer according to any one of items [1] to [3], further comprising a structural unit represented by formula (1-1), [Chemical formula] In formula (1-1), R 21 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, When Q is the alkyl group and X is the alkylene group, Q and X may condense to form a cyclic group, a polymer. [5] The polymer according to any one of items [1] to [4], further comprising a structural unit represented by formula (1-4), [Chemical formula] In formula (1-4), R 22 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, a polymer. [6] The polymer according to any one of [1] to [5], further comprising at least one selected from the structural unit represented by formula (1) and the structural unit represented by formula (2), [Chemical formula] In formula (1), R p is a group having two or more (meth)acryloyl groups, and R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, [Chemical formula] In formula (2), R s is a group having one (meth)acryloyl group, and R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, a polymer. [7] The polymer according to any one of [1] to [6], further comprising the structural unit represented by formula (3), [Chemical formula] In formula (3), R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, a polymer. [8] The polymer according to [4], further comprising at least one selected from the structural unit represented by formula (8) and the structural unit represented by formula (9), [Chemical formula] In formula (8), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, When Q is the alkyl group and X is the alkylene group, Q and X may condense to form a cyclic group. R p is a group having two or more (meth)acryloyl groups. R 21 and R 22 are a hydrogen atom or an organic group having 1 to 3 carbon atoms.

Chemical formula

Chemical formula

[10] The polymer according to item [4], further comprising a structural unit represented by formula (6),

Chemical formula

[11] The polymer according to any one of items [1] to

[10] , further comprising a structural unit represented by formula (MA),

Chemical formula

[12] The polymer according to any one of items [1] to

[11] , the polymer contains a structural unit represented by the formula (1-2), R in the formula (1-2) p is at least one selected from the group represented by formula (1b), the group represented by formula (1c), and the group represented by formula (1d),

Chemical formula

[13] The polymer according to any one of items [1] to

[12] , wherein the polymer contains a structural unit represented by the formula (1-3), R in the formula (1-3) s is a group represented by the formula (2a), [Chemical formula] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group, a polymer. The polymer according to any one of items [1] to

[13] of

[14] , wherein the polymer has a structure represented by formula (P1), [Chemical formula] In formula (P1), n is an integer from 1 to 6, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monofunctional or polyfunctional thiol group-containing compound-derived organic group having 1 to 30 carbon atoms and 1 to 6 valences, B contains at least one structural unit selected from the structural unit represented by the above formula (1-2) and the structural unit represented by the above formula (1-3), and a plurality of Bs may be the same or different, a polymer. The polymer according to item [2] of

[15] , wherein the polymer has a structure represented by formula (P2), [Chemical formula] In formula (P2), n is an integer from 1 to 6, p and q represent the molar contents of the structural units A and B contained in each polymer chain within n [ ], p and q may be the same or different for each polymer chain within n [ ], p + q = 1, p is 0 or more, and q is 0 or more, When the molar contents of the respective structural units A and B contained in the polymer are p t and q t respectively, then p t + q t = 1, p t is greater than 0, and q tis greater than 0, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monofunctional or polyfunctional organic group having 1 to 6 valences and 1 to 30 carbon atoms derived from a thiol group-containing compound, A represents at least one structural unit selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), the structural unit represented by the formula (IN), the structural unit represented by the formula (AK), and the structural unit represented by the formula (CA), B contains at least one structural unit selected from the structural unit represented by the formula (1-2) and the structural unit represented by the formula (1-3), A polymer in which a plurality of As and Bs may be the same or different. The polymer according to item [3] of

[16] , The polymer has a structure represented by the formula (P3), [Chemical formula] In the formula (P3), n is an integer from 1 to 6, p, q, and r represent the molar contents of the structural units A, B, and C contained in each polymer chain within the n [ ], p, q, and r may be the same or different for each polymer chain within the n [ ], p + q + r = 1, p is 0 or more, q is 0 or more, and r is 0 or more, Regarding the molar contents of the respective structural units A, B, and C contained in the polymer as p t , q t and r t respectively, then p t + q t + r t = 1, p t is greater than 0, q t is greater than 0, r t is greater than 0, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound, A represents at least one structural unit selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), the structural unit represented by the formula (IN), the structural unit represented by the formula (AK), and the structural unit represented by the formula (CA), B contains at least one structural unit selected from the structural unit represented by the formula (1-2) and the structural unit represented by the formula (1-3), C represents at least one structural unit selected from the structural unit represented by the formula (MI) and the structural unit represented by the formula (AD), A polymer in which a plurality of As, Bs, and Cs may be the same or different. The polymer according to any one of items [1] to

[16] of

[17] , The weight average molecular weight of the polymer is 2,000 or more and 50,000 or less.

[18] Any one of items [1] to

[17] The polymer according to claim 1, The melting point of the polymer is 20°C or more and 130°C or less. A polymer solution containing the polymer according to any one of items [1] to

[18] of

[19] . The polymer solution according to item

[19] of

[20] , Further containing a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof. The polymer solution according to item

[19] or

[20] of

[21] , A polymer solution used for forming a color filter, a black matrix, a spacer, or a partition wall material.

[22] The polymer according to any one of items [1] to

[16] , And a photo radical polymerization initiator. A photosensitive resin composition. A cured product formed from the photosensitive resin composition according to item

[22] of

[23] . A polymer containing a structural unit represented by formula (MA), wherein the softening point of the polymer is 20°C or higher and 158°C or lower,

Chem.

[24] , further comprising at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), the structural unit represented by formula (IN), the structural unit represented by formula (AK), and the structural unit represented by formula (CA),

Chem.

Chem.

Chem.

Chem.

[25] of

[26] , further comprising at least one structural unit selected from the structural unit represented by formula (MI) and the structural unit represented by formula (AD), [Chemical formula] In formula (MI), R 31 is a hydrogen atom or an organic group having 1 to 30 carbon atoms, R 32 and R 33 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, [Chemical formula] In formula (AD), R 11 and R 12 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, and R 13 and R 14 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a polymer. The polymer according to item

[24] of

[27] , The polymer has a structure represented by formula (P1'), [Chemical formula] In formula (P1'), n is an integer from 1 to 6, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monofunctional or polyfunctional thiol group-containing compound-derived organic group having 1 to 30 carbon atoms and 1 to 6 valences, B represents a structural unit represented by the above formula (MA), a polymer. The polymer according to item

[25] of

[27] , The polymer has a structure represented by formula (P2'), [Chemical formula] In formula (P2'), n is an integer from 1 to 6, p and q' represent the molar contents of the structural units A and B' contained in each polymer chain within n [ ], p and q' may be the same or different for each polymer chain within n [ ], p + q' = 1, p is 0 or more, and q' is 0 or more, Regarding the molar contents of the respective structural units A and B' contained in the polymer as p t , and q t ', then p t + q t ' = 1, p t is greater than 0, and qt ' is greater than 0, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound, A represents at least one structural unit selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), the structural unit represented by the formula (IN), the structural unit represented by the formula (AK), and the structural unit represented by the formula (CA), B' represents the structural unit represented by the formula (MA), A plurality of As and B's may be the same or different, a polymer. The polymer according to item

[26] of

[28] , The polymer has a structure represented by the formula (P3'),

Chemical formula

Advantages of the Invention

[0007] According to the present invention, there is provided a polymer as a resin material for use in a photosensitive resin composition that has a low softening point and melting point, thus excellent pattern formability after curing, has high alkali solubility, thus excellent developability, and has reduced yellowing, thus high heat discoloration resistance.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Embodiments for Carrying Out the Invention

[0009] Hereinafter, embodiments of the present invention will be described. In all the drawings, similar components are denoted by similar reference numerals, and the description will be omitted as appropriate. Also, all the drawings are for illustrative purposes only. The shapes and dimensional ratios of the respective members in the drawings do not necessarily correspond to actual articles. In this specification, the notation "a~b" in the description of a numerical range means "a or more and b or less" unless otherwise specified. For example, "5~90%" means "5% or more and 90% or less".

[0010] In the notation of a group (atomic group) in this specification, a notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[0011] The notation "(meth)acryl" in this specification represents a concept that includes both acryl and methacryl. The same applies to similar notations such as "(meth)acrylate". In particular, the "(meth)acryloyl group" in this specification represents a concept that includes an acryloyl group represented by -C(=O)-CH=CH2 and a methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0012] [Polymer P] The polymer of the present invention (referred to as "Polymer P" in this specification) will be described. Unless otherwise specified, throughout all embodiments, structural units or compounds represented by the same structural formula have a common definition, and the preferred embodiments are the same as well.

[0013] <First Embodiment> (Polymer P(I)) The polymer of the present invention according to the first embodiment (referred to as "polymer P(I)" in this specification) contains at least one structural unit selected from the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3). Alternatively, the softening point of the polymer P(I) of this embodiment is 0°C or higher and 100°C or lower.

[0014]

Chemical formula

[0015] In formula (1-2), R p is a group having two or more (meth)acryloyl groups, and R 22 is a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0016]

Chemical formula

[0017] In formula (1-3), R s is a group having one (meth)acryloyl group, and R 22 is a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0018] The polymer P(I) of this embodiment has a low softening point in the range of 0°C or higher and 100°C or lower. The softening point of the polymer P(I) is preferably 0°C or higher and 90°C or lower, and more preferably 0°C or higher and 80°C or lower. A photosensitive resin composition containing such a polymer P(I) having a low softening point is excellent in processability and pattern formability in photolithography processing. The softening point of the polymer P(I) of this embodiment can be adjusted by appropriately selecting the structural units constituting the polymer P(I).

[0019] The polymer P(I) of the present embodiment contains a structural unit represented by formula (1-2) and / or a structural unit represented by formula (1-3). In other words, the polymer P(I) contains either one or both of the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3). Thereby, the photosensitive resin composition containing the polymer P(I) has excellent sensitivity when subjected to photolithography processing. This is presumably because the (meth)acryloyl group contained in the structural unit represented by formula (1-2) or formula (1-3) promotes the curing reaction (polymerization reaction).

[0020] In formula (1-2) or formula (1-3), R 22 Examples of the organic group having 1 to 3 carbon atoms that can constitute R include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R 21 and R 22 are both preferably hydrogen atoms.

[0021] In the structural unit represented by formula (1-2), R p is a group containing two or more (meth)acryloyl groups, preferably a group containing 2 to 9 (meth)acryloyl groups, and more preferably a group containing 3 to 6 (meth)acryloyl groups. By optimizing the number of (meth)acryloyl groups contained in R p , the sensitivity of the polymer P(I) containing this in the exposure process can be further enhanced. Also, it becomes easier to achieve a higher degree of compatibility between the sensitivity and the alkali solubility of the polymer P(I). Furthermore, the heat resistance of the polymer P(I) can be improved.

[0022] R p in formula (1-2) is preferably a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d), and contains at least one selected from these. By being such a group, there is a tendency to easily obtain the above various effects.

[0023]

Chemical formula

[0024] In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different, X 1 is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and a plurality of Xs present 1 may be the same or different, X 1 ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z' (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO), X 2 is a (k + 1)-valent organic group having 1 to 12 carbon atoms. R is preferably a hydrogen atom from the viewpoint of further improving the sensitivity (ease of polymerization). k may be 2 or 3, but is preferably 3 from the viewpoints of availability of raw materials and further improvement of sensitivity.

[0025] X 1 When is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 When is an alkylene group having 1 to 6 carbon atoms, X 1 is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and still more preferably -CH2- (methylene group).

[0026] X 1 When is a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms of X may be linear or branched. The alkylene group having 1 to 6 carbon atoms for X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and even more preferably -CH2-CH2- (ethylene group) or -CH2-CH(CH3)-.

[0027] X 1 When 'is an alkylene group having 1 to 6 carbon atoms, the specific embodiments thereof are the same as those of X 1 and the like. X 1 When 'is a group represented by -X'-Z', the specific embodiments of X' are the same as those of X above.

[0028] X 2 As the (k + 1)-valent organic group having 1 to 12 carbon atoms for X, any group obtained by removing (k + 1) hydrogen atoms from any organic compound can be mentioned. Here, the "any organic compound" is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less. X 2 X is, for example, a group obtained by removing (k + 1) hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group obtained by removing (k + 1) hydrogen atoms from a linear hydrocarbon having 1 to 3 carbon atoms. Here, the hydrocarbon may contain an oxygen atom (such as an ether bond or a hydroxy group). Further, the hydrocarbon is preferably a saturated hydrocarbon. In another embodiment, X 2 may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure and a group containing a heterocyclic structure (such as an isocyanuric acid structure).

[0029]

Chemical formula

[0030] In formula (1c), k, R, X 1 and X 2 are, respectively, R, k, X in formula (1b) 1and X 2 is synonymous with, and the plurality of Rs may be the same as or different from each other, and the plurality of Xs 1 may be the same as or different from each other, X 3 is a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms, X 6 is a divalent organic group having 1 to 6 carbon atoms.

[0031] R, k, X 1 and X 2 For the specific embodiments, preferred embodiments, etc. of, it is the same as those described in formula (1b). X 3 and X 6 Examples of the divalent organic group having 1 to 6 carbon atoms of and may include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. Here, the hydrocarbon may contain an oxygen atom (such as an ether bond or a hydroxy group). Further, the hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 Examples of the divalent organic group having 1 to 6 carbon atoms of and may include a linear or branched alkylene group. The number of carbon atoms of the linear or branched alkylene group is preferably 1 to 3.

[0032]

Chemical formula

[0033] In formula (1d), n is an integer of 2 to 5, and preferably 2 or 3. For the specific embodiments, preferred embodiments, etc. of R, it is the same as those described in formula (1b).

[0034] When the polymer P(I) contains a structural unit represented by the formula (1-2), the proportion of the structural unit represented by the formula (1-2) in all the structural units of the polymer P(I) is preferably 3 to 40 mol%, more preferably 3 to 30 mol%.

[0035] In the structural unit represented by the formula (1-3) that can constitute the polymer P(I), R S is a group containing only one (meth)acryloyl group. In particular, in the design of a normal photosensitive resin composition, when trying to increase the curability to raise the sensitivity, the curing often proceeds too much and the developability tends to deteriorate. On the other hand, when trying to improve the developability, the curing often becomes insufficient. Therefore, the polymer P(I) preferably contains either or both of the structural unit represented by the formula (1-2) and the structural unit represented by the formula (1-3), whereby both the sensitivity and the developability can be achieved in a good balance.

[0036] R S is, for example, a group represented by the following formula (2a).

[0037]

Chemical formula

[0038] In the formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. The total carbon number of X 10 is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. X 10 As the divalent organic group of X, for example, an alkylene group is preferable. Some -CH2- in this alkylene group may be an ether group (-O-). The alkylene group may be linear or branched, but is more preferably linear.

[0039] X 10 is more preferably a linear alkylene group having a total carbon number of 3 to 6 as the divalent organic group of X. The carbon number of X 10 (the carbon number of X 10By appropriately selecting the chain length), the structural unit represented by formula (2) is more likely to participate in the cross-linking reaction, and the sensitivity can be enhanced.

[0040] X 10 The divalent organic group (e.g., alkylene group) of may be optionally substituted with any substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, etc. Also, X 10 The divalent organic group of may be any group other than an alkylene group. For example, it may be a divalent group formed by linking one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group, etc.

[0041] In addition to the above structural unit, the polymer P(I) of this embodiment may contain at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), the structural unit represented by formula (IN), the structural unit represented by formula (AK), and the structural unit represented by formula (CA).

[0042]

Chemical formula

[0043] In formula (NB), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2.

[0044]

Chemical formula

[0045] In formula (ST), R 40 , R 41 and R 42 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R 43is, independently, a hydrogen atom or an organic group having 1 to 30 carbon atoms.

[0046]

Chem.

[0047] In formula (IN), R 61 ~R 68 is, independently, a hydrogen atom or an organic group having 1 to 30 carbon atoms.

[0048]

Chem.

[0049] In formula (AK), at least one of R 71 , R 72 , R 73 and R 74 is a linear or branched alkyl group having 3 or more carbon atoms, and the rest of R 71 , R 72 , R 73 and R 74 is, independently, a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.

[0050]

Chem.

[0051] In formula (CA), X 51 is a single bond or a linear or branched alkylene group having 1 or more carbon atoms, when X 51 is a single bond, at least one of R 51 , R 52 and R 53 is a linear or branched alkyl group having 2 or more carbon atoms, and the rest of R 51 , R 52 and R 53 is a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, X51 When it is a linear or branched alkyl group having 1 or more carbon atoms, R 51 , R 52 and R 13 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.

[0052] When the polymer P(I) contains a structural unit represented by the formula (NB), the proportion of the structural unit represented by the formula (NB) in all the structural units constituting the polymer P(I) is preferably 25 to 75 mol%, more preferably 30 to 65 mol%, and still more preferably 35 to 60 mol%. The norbornene-derived structural unit represented by the formula (NB) is chemically robust. Therefore, the polymer P(I) containing this as a structural unit has a small weight loss when subjected to heat treatment and is stable. Thus, the photosensitive resin composition containing the polymer P(I) containing the structural unit represented by the formula (NB) can be suitably used for producing films and filters for liquid crystal display devices and solid-state imaging devices that require heat resistance. By setting the proportion of the structural unit represented by the formula (NB) in the polymer P(I) within the above range, the heat resistance of the polymer P(I) can be improved, and the balance of sensitivity, alkali solubility, and heat discoloration resistance can be improved at a high level.

[0053] In the structural unit represented by the above formula (NB) that can constitute the polymer P(I), R 1 ~R 4 Examples of the organic group having 1 to 30 carbon atoms that can constitute include saturated or unsaturated, linear, branched, or cyclic hydrocarbon groups having 1 to 30 carbon atoms, alkoxy groups, and heterocyclic groups, as well as carboxy groups and the like. Examples of the hydrocarbon group include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, and cycloalkyl groups.

[0054] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like.

[0055] Examples of the alkenyl group include an allyl group, a pentenyl group, a vinyl group, and the like. Examples of the alkynyl group include an ethynyl group, and the like. Examples of the alkylidene group include a methylidene group, an ethylidene group, and the like. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, an anthracenyl group.

[0056] Examples of the aralkyl group include a benzyl group, a phenethyl group, and the like. Examples of the alkaryl group include a tolyl group, a xylyl group, and the like. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, an n-hexyloxy group, and the like. Examples of the heterocyclic group include an epoxy group, an oxetanyl group, and the like.

[0057] In the structural unit represented by the formula (NB), R 1 , R 2 , R 3 and R 4 are preferably hydrogen or an alkyl group, and more preferably hydrogen. In addition, R 1 , R 2 , R 3 and R 4The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted by any atomic group. For example, they may be substituted by a fluorine atom, a hydroxy group, a carboxy group, etc. More specifically, R 1 、R 2 、R 3 and R 4 As the organic group having 1 to 30 carbon atoms, an alkyl fluoride group or the like may be selected. In the structural unit represented by the formula (NB), a1 is preferably 0 or 1, more preferably 0.

[0058] When the polymer P(I) contains the structural unit represented by the formula (ST), the proportion of the structural unit represented by the formula (ST) in all the structural units constituting the polymer P(I) is preferably 25 to 75 mol%, more preferably 30 to 65 mol%, still more preferably 35 to 60 mol%. The structural unit represented by the formula (ST) is chemically robust. Therefore, the polymer P(I) containing this as a structural unit has little weight loss when subjected to heat treatment and is stable. Thus, the photosensitive resin composition containing the polymer P(I) containing the structural unit represented by the formula (ST) can be suitably used for producing films and filters for liquid crystal display devices and solid-state imaging devices that require heat resistance. By setting the proportion of the structural unit represented by the formula (ST) in the polymer P(I) within the above range, the heat resistance of the polymer P(I) can be improved, and the balance of sensitivity, alkali solubility, and heat discoloration resistance can be improved at a high level.

[0059] In the structural unit represented by the formula (ST) that can constitute the polymer P(I), R 40 、R 41 and R 42 Examples of the organic group having 1 to 3 carbon atoms that can constitute include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R 40 、R 41 and R 42 are preferably hydrogen atoms.

[0060] R 43Examples of the organic group having 1 to 30 carbon atoms that can constitute include saturated or unsaturated, linear, branched or cyclic hydrocarbon groups having 1 to 30 carbon atoms, alkoxy groups, heterocyclic groups, and carboxy groups. Examples of the hydrocarbon group include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, and cycloalkyl groups.

[0061] Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

[0062] Examples of the alkenyl group include allyl group, pentenyl group, vinyl group and the like. Examples of the alkynyl group include ethynyl group and the like. Examples of the alkylidene group include methylidene group, ethylidene group and the like. Examples of the aryl group include tolyl group, xylyl group, phenyl group, naphthyl group, anthracenyl group.

[0063] Examples of the aralkyl group include benzyl group, phenethyl group and the like. Examples of the alkaryl group include tolyl group, xylyl group and the like. Examples of the cycloalkyl group include adamantyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group and the like. Examples of the heterocyclic group include epoxy group, oxetanyl group and the like.

[0064] R in the structural unit represented by formula (ST) 43 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. In addition, the hydrogen atom in the organic group having 1 to 30 carbon atoms of R 43 may be substituted by any atomic group. For example, it may be substituted by a fluorine atom, a hydroxy group, a carboxy group, etc. More specifically, as the organic group having 1 to 30 carbon atoms of R 43 , an alkyl fluoride group or the like may be selected.

[0065] When the polymer P(I) contains a structural unit represented by formula (IN), the proportion of the structural unit represented by formula (IN) in all the structural units constituting the polymer P(I) is preferably 5 to 30 mol%, more preferably 6 to 28 mol%, still more preferably 7 to 25 mol%. The structural unit represented by formula (IN) is chemically robust. Therefore, the polymer P(I) containing this as a structural unit has a small weight loss when subjected to heat treatment and is stable. Thus, the photosensitive resin composition containing the polymer P(I) can be suitably used for producing films and filters for use in liquid crystal display devices and solid-state imaging devices that require heat resistance.

[0066] In the indenyl-derived structural unit represented by formula (IN) that can constitute the polymer P(I), R 61 ~R 68 Examples of the organic group having 1 to 30 carbon atoms that can constitute include saturated or unsaturated, linear, branched or cyclic hydrocarbon groups having 1 to 30 carbon atoms, alkoxy groups, and heterocyclic groups, and carboxy groups. Examples of the hydrocarbon group include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, and cycloalkyl groups.

[0067] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like.

[0068] Examples of the alkenyl group include an allyl group, a pentenyl group, a vinyl group, and the like. Examples of the alkynyl group include an ethynyl group, and the like. Examples of the alkylidene group include a methylidene group, an ethylidene group, and the like. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, an anthracenyl group.

[0069] Examples of the aralkyl group include a benzyl group, a phenethyl group, and the like. Examples of the alkaryl group include a tolyl group, a xylyl group, and the like. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, an n-hexyloxy group, and the like. Examples of the heterocyclic group include an epoxy group, an oxetanyl group, and the like. In the structural unit represented by formula (IN), R 61 ~R 8 is preferably hydrogen or an alkyl group, more preferably hydrogen. Note that the hydrogen atom in the organic group having 1 to 30 carbon atoms of R 1 ~R 8 may be substituted with any atomic group. For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, R 1 ~R 68As the organic group having 1 to 30 carbon atoms, an alkyl fluoride group or the like may be selected.

[0070] When the polymer P(I) contains a structural unit represented by the formula (AK), the proportion of the structural unit represented by the formula (AK) in all the structural units constituting the polymer P(I) is preferably 2 to 60 mol%, more preferably 3 to 55 mol%, and still more preferably 5 to 50 mol%. By setting the proportion of the structural unit represented by the formula (AK) in the polymer P(I) within the above range, a polymer P(I) having a low softening point and a low melting point and having an improved balance of sensitivity, alkali solubility, and heat discoloration resistance at a high level can be obtained.

[0071] In the structural unit represented by the formula (AK) that can constitute the polymer P(I), R 71 、R 72 、R 73 and R 74 At least one of is a linear or branched alkyl group having 3 or more carbon atoms, preferably a linear or branched alkyl group having 4 or more carbon atoms, more preferably a linear or branched alkyl group having 5 or more carbon atoms, and still more preferably a linear or branched alkyl group having 6 or more carbon atoms. R 71 、R 72 、R 73 and R 74 The rest of are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms. R 71 、R 72 、R 73 and R 74 The upper limit of the number of carbon atoms of the linear or branched alkyl group having 3 or more carbon atoms that constitutes at least one of is, for example, 30 or less carbon atoms, preferably 25 or less carbon atoms, and more preferably 20 or less carbon atoms. Among them, since the structural unit represented by the formula (AK) is easily introduced into the polymer P(I), the molecular design is easy, and the resulting polymer P(I) has a low softening point and a low melting point without impairing the heat yellowing resistance. In the structural unit represented by the formula (AK), R 71 、R 72 、R 73 and R74 One of them is a linear or branched alkyl group having 3 or more carbon atoms, and R 71 , R 72 , R 73 and R 74 The remaining three of are preferably hydrogen atoms. More preferably, in the structural unit represented by the formula (AK), R 71 , R 72 , R 73 and R 74 One of is a linear or branched alkyl group having 3 or more carbon atoms, and R 71 , R 72 , R 73 and R 74 One of is a linear alkyl group having 3 or more carbon atoms, and R 71 , R 72 , R 73 and R 74 The remaining three of are hydrogen atoms. R 71 , R 72 , R 73 and R 74 The larger the number of carbon atoms of the linear or branched alkyl group having 3 or more carbon atoms that constitutes at least one of R , R , R and R , the lower the softening point and melting point of the resulting polymer P(I) tend to be. Therefore, according to the desired softening point or melting point in the use of the polymer P(I), the number of carbon atoms of the structural unit of the formula (AK) can be selected.

[0072] When the polymer P(I) contains a structural unit represented by the formula (CA), the proportion of the structural unit represented by the formula (CA) in all the structural units constituting the polymer P(I) is preferably 2 to 30 mol%, more preferably 3 to 28 mol%, and still more preferably 5 to 25 mol%. By setting the proportion of the structural unit represented by the formula (CA) in the polymer P(I) within the above range, a polymer P(I) having a low softening point and a low melting point and having an improved balance of sensitivity, alkali solubility, and heat discoloration resistance at a high level can be obtained.

[0073] By introducing a structural unit (CA) derived from a carboxylic acid-containing alkene into the polymer P(I), the softening point and melting point of the polymer P(I) can be lowered without accompanying changes in sensitivity, alkali solubility, and heat-resistant yellowing properties. As a result, the polymer P(I) containing the structural unit (CA) derived from a carboxylic acid-containing alkene is easily melted by heat during curing and has excellent processability and pattern formability in photolithography processing. Therefore, the photosensitive resin composition containing the polymer P(I) can be suitably used for producing films and filters for use in liquid crystal display devices and solid-state imaging devices that require heat resistance.

[0074] In the structural unit represented by the formula (CA) that can constitute the polymer P(I), X 51 is a single bond or a linear or branched alkylene group having 1 or more carbon atoms, X 51 When is a single bond, R 51 , R 52 and R 53 At least one of is a linear or branched alkyl group having 2 or more carbon atoms, and the rest of R 51 , R 52 and R 53 is a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, X 51 When is a linear or branched alkyl group having 1 or more carbon atoms, R 51 , R 52 and R 53 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms.

[0075] In a preferred embodiment, in the structural unit represented by the formula (CA), X 51 is a linear or branched alkylene group having 1 or more carbon atoms, and R 51 , R 52 and R 53 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms. As another preferred embodiment, X 51is a linear or branched alkylene group having 1 or more carbon atoms, and R 51 、R 52 and R 53 are hydrogen atoms. X 51 In the aspect where is a linear or branched alkylene group having 1 or more carbon atoms, X 51 is more preferably a linear alkylene group having 1 or more carbon atoms, still more preferably a linear alkylene group having 2 or more carbon atoms, and even more preferably a linear alkylene group having 3 or more carbon atoms. X 51 The upper limit of the number of carbon atoms of the linear or branched alkylene group having 1 or more carbon atoms constituting is, for example, 30 or less, preferably 25 or less, and more preferably 20 or less.

[0076] In still another aspect, in the structural unit represented by the formula (CA), X 51 is a single bond, and at least one of R 51 、R 52 and R 53 is a linear or branched alkyl group having 2 or more carbon atoms, and the remainder of R 51 、R 52 and R 53 is a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms. More preferably, X 51 is a single bond, 5 1 is a linear or branched alkyl group having 2 or more carbon atoms, and R 52 and R 53 are hydrogen atoms.

[0077] Among them, in the structural unit represented by the formula (CA), it is easy to introduce the structural unit into the polymer P(I), so molecular design is easy, and the obtained polymer P(I) has a low softening point and a low melting point without impairing heat-resistant yellowness. Therefore, in the structural unit represented by the formula (CA), X 51 is a linear or branched alkylene group having 1 or more carbon atoms, and R 51 、R 52 and R 53 are preferably hydrogen atoms. X51 The larger the number of carbon atoms in the alkylene group constituting 51 , the lower the softening point and melting point of the resulting polymer P(I) tend to be. Therefore, the number of carbon atoms in the structural unit of formula (CA) can be selected according to the desired softening point or melting point in the application of the polymer P(I).

[0078] In addition to the above structural unit, the polymer P(I) of the present embodiment may further contain at least one structural unit selected from the structural unit represented by formula (MI) and the structural unit represented by formula (AD).

[0079]

Chemical formula

[0080] In formula (MI), R 31 is a hydrogen atom or an organic group having 1 to 30 carbon atoms, R 32 and R 33 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0081]

Chemical formula

[0082] In formula (AD), R 11 and R 12 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, and R 13 and R 14 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0083] When the polymer P(I) contains a structural unit represented by the formula (MI), the proportion of the structural unit represented by the formula (MI) in all the structural units constituting the polymer P(I) is preferably 1 to 30 mol%, more preferably 1.5 to 28 mol%, and still more preferably 2 to 25 mol%. By setting the proportion of the structural unit represented by the formula (MI) in the polymer P(I) within the above range, the balance of the sensitivity, alkali solubility, and heat discoloration resistance of the polymer P(I) can be improved to a high level.

[0084] In the structural unit represented by the above formula (MI) that can constitute the polymer P(I), R 31 is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R 32 and R 33 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. In the structural unit represented by the formula (MI), R 32 and R 33 Examples of the organic group having 1 to 3 carbon atoms that can constitute include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R 32 and R 33 are preferably hydrogen atoms. Examples of the organic group having 1 to 30 carbon atoms that can constitute R 31 in the formula (MI) include saturated or unsaturated, linear, branched, or cyclic hydrocarbon groups having 1 to 30 carbon atoms, alkoxy groups, and heterocyclic groups, as well as carboxy groups and the like. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, and a cycloalkyl group. R 31 is preferably a hydrocarbon group having 1 to 25 carbon atoms, more preferably a hydrocarbon group having 1 to 20 carbon atoms, and still more preferably a hydrocarbon group having 1 to 15 carbon atoms.

[0085] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like.

[0086] Examples of the alkenyl group include an allyl group, a pentenyl group, a vinyl group, and the like. Examples of the alkynyl group include an ethynyl group, and the like. Examples of the alkylidene group include a methylidene group, an ethylidene group, and the like. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, an anthracenyl group.

[0087] Examples of the aralkyl group include a benzyl group, a phenethyl group, and the like. Examples of the alkaryl group include a tolyl group, a xylyl group, and the like. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, an n-hexyloxy group, and the like. Examples of the heterocyclic group include an epoxy group, an oxetanyl group, and the like.

[0088] R in the structural unit represented by the formula (MI) 31 is preferably a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. R in the structural unit represented by the formula (MI) 31 R 32 and R 33 are appropriately selected. In particular, by selecting R 31 the alkali solubility of the resulting polymer P(I) can be adjusted. For example, R31 By using a hydrogen atom, the alkali solubility of the resulting polymer P(I) can be improved. Also, R 31 By using an alkyl group, a cycloalkyl group, or an aryl group, the alkali solubility of the resulting polymer P(I) can be suppressed. These substituents in the structural unit represented by formula (MI) can be selected according to the desired alkali solubility for the use of the polymer P(I). In addition, R 31 The hydrogen atom in the organic group having 1 to 30 carbon atoms of R may be substituted with any atomic group. For example, it may be substituted with a fluorine atom, a hydroxy group, a carboxy group, etc. More specifically, R 31 may be selected as an organic group having 1 to 30 carbon atoms, such as a perfluoroalkyl group.

[0089] When the polymer P(I) contains a structural unit represented by formula (AD), the proportion of the structural unit represented by formula (AD) in all the structural units constituting the polymer P(I) is preferably 2 to 30 mol%, more preferably 3 to 28 mol%, still more preferably 5 to 25 mol%. By setting the proportion of the structural unit represented by formula (AD) in the polymer P(I) within the above range, a polymer P(I) having a low softening point and a low melting point and an improved balance of sensitivity, alkali solubility, and heat discoloration resistance at a high level can be obtained.

[0090] By introducing a structural unit (AD) derived from an unsaturated carboxylic acid dialkyl ester into the polymer P(I), the softening point and melting point of the polymer P(I) can be lowered without accompanying changes in sensitivity, alkali solubility, and heat yellowing resistance. Thereby, the polymer P(I) having a structural unit (AD) derived from an unsaturated carboxylic acid dialkyl ester is easily melted by heat during curing and has excellent processability and pattern formability in photolithography processing. Therefore, the photosensitive resin composition containing the polymer P(I) can be suitably used for manufacturing films and filters for use in liquid crystal display devices and solid-state imaging devices that require heat resistance.

[0091] In the structural unit derived from the unsaturated carboxylic acid dialkyl ester represented by the formula (AD), -C(=O)-O-R 11 group and -C(=O)-O-R 12 The configuration between the groups is not limited and may be cis or trans. More specifically, as described in the method for producing the following polymer P(I), the structural unit derived from the unsaturated carboxylic acid dialkyl ester represented by the formula (AD) may be a structure derived from a cis-unsaturated dicarboxylic acid dialkyl ester or a structure derived from a trans-unsaturated dicarboxylic acid dialkyl ester.

[0092] In the structural unit represented by the above formula (AD) that can constitute the polymer P(I), R 11 and R 12 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms. R in the structural unit of the formula (AD) 11 and R 12 Examples of the linear or branched alkyl group having 1 to 12 carbon atoms that can constitute include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. Among them, since the resulting polymer P(I) has a low softening point and a low melting point without impairing heat-resistant yellowness, R 11 and R 12 are preferably linear or branched alkyl groups having 1 to 12 carbon atoms. In the structural unit represented by the above formula (AD) that constitutes the polymer P(I), R 13 and R 14 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group. From the viewpoint of reactivity, R 13 and R 14 are preferably hydrogen atoms.

[0093] In addition to the above structural units, the polymer P(I) of the present embodiment may contain a structural unit represented by formula (1-1).

[0094]

Chemical formula

[0095] In the structural unit represented by formula (1-1), R 21 is a hydrogen atom or an organic group having 1 to 3 carbon atoms. Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of this alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Examples of the substituent of the substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group, etc. X represents an oxygen atom or a substituted or unsubstituted alkylene having 1 to 4 carbon atoms. Examples of the alkylene group constituting X include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the substituent of the substituted alkylene group having 1 to 4 carbon atoms include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group, etc. When Q is an alkyl group and X is an alkylene group, any carbon atom of the alkyl group of Q and the alkylene group of X may be bonded to form a ring. Examples of the ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a benzene ring, a naphthalene ring, etc. In formula (1-1), an embodiment in which X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group, or an embodiment in which X is an oxygen atom and Z is a (meth)acryloyl group is preferably used.

[0096] More specifically, in formula (1-1), an embodiment where X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group represented by the following formula (1a), or an embodiment where X is an oxygen atom and Z is an acryloyl group (-C(=O)-CH=CH2) or a methacryloyl group (-C(=O)-C(CH3)=CH2) is preferably used.

[0097]

Chemical formula

[0098] In formula (1a), R is a hydrogen atom or a methyl group.

[0099] When the polymer P(I) contains a structural unit represented by formula (1-1), the proportion of the structural unit represented by formula (1-1) in all the structural units of the polymer P(I) is preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%.

[0100] The polymer P(I) may contain a structural unit represented by formula (1-4).

[0101]

Chemical formula

[0102] In formula (1-4), R 22 is a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0103] When the polymer P(I) contains the structural unit of formula (1-1) and the structural unit of formula (1-4), the polymer P(I) will have both a (meth)acryloyl group (the “-Z” group in formula (1-1)) and a carboxyl group represented by formula (1-4). This (meth)acryloyl group contains a polymerizable carbon-carbon double bond. Thus, since the polymerizable group and the carboxyl group are present in the same polymer molecule, the polymer P(I) can be designed to have relatively large values for the double bond equivalent and the acid value. In other resins such as (meth)acrylic resins, it is difficult to increase the content of both the polymerizable group and the carboxyl group. By having such a structure, the polymer P can achieve both high sensitivity and developability at a high level.

[0104] The polymer P(I) may contain at least one selected from the structural unit represented by formula (1) and the structural unit represented by formula (2).

[0105]

Chemical formula

[0106]

Chemical formula

[0107] In formula (1) and formula (2), R p and R s , and also R 21 and R 22 are synonymous with those in the above formula (1-1), formula (1-2) and formula (1-4).

[0108] When the polymer P(I) contains the structural unit represented by formula (1), the proportion of the structural unit represented by formula (1) in all the structural units of the polymer P(I) is preferably 0.5 to 25 mol%, more preferably 1 to 18 mol%.

[0109] When the polymer P(I) contains a structural unit represented by the formula (2), the proportion of the structural unit represented by the formula (2) in all the structural units of the polymer P(I) is preferably 0.5 to 35 mol%, more preferably 2 to 25 mol%.

[0110] In addition to the above structural unit, the polymer P(I) of the present embodiment may contain a structural unit represented by the formula (3). By containing the structural unit represented by the formula (3), the polymer P(I) has high alkali solubility. As a result, when the photosensitive resin composition containing the polymer P(I) is subjected to a photolithography method using an aqueous alkali solution as a developer, it has excellent developability. The proportion of the structural unit represented by the formula (3) in all the structural units of the polymer P(I) is preferably 1 to 10 mol%, more preferably 2 to 7 mol%.

[0111]

Chemical formula

[0112] In the formula (3), R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0113] The polymer P can contain at least one of the structural unit represented by the formula (8) and the structural unit represented by the formula (9). Here, the structural unit of the formula (8) is a structural unit composed of the structural unit represented by the formula (1-1) and the structural unit represented by the formula (1-2), and the structural unit of the formula (9) is a structural unit composed of the structural unit represented by the formula (1-1) and the structural unit represented by the formula (1-3).

[0114]

Chemical formula

[0115]

Chemical formula

[0116] In formula (8), Q, X, and Z are synonymous with formula (1-1), and R p is synonymous with formula (1-2). In formula (9), Z, Q, and X are synonymous with formula (1-1), and R S is synonymous with formula (1-3).

[0117] When the polymer P(I) contains a structural unit represented by formula (8), the proportion of the structural unit represented by formula (8) in all the structural units of the polymer P(I) is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%. When the polymer P(I) contains a structural unit represented by formula (9), the proportion of the structural unit represented by formula (9) in all the structural units of the polymer P(I) is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%.

[0118] The polymer P(I) can contain a structural unit represented by the following formula (5) composed of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-4). By containing this structural unit, both sensitivity and developability can be achieved with a better balance.

[0119]

Chemical formula

[0120] In formula (5), Z, X, and Q are synonymous with formula (1-1) and formula (1-4). When the polymer P(I) contains a structural unit represented by formula (5), the proportion of the structural unit represented by formula (5) in all the structural units of the polymer P(I) is preferably 1 to 12 mol%, more preferably 1 to 9 mol%.

[0121] From the viewpoint of the effects of the present invention, the polymer P(I) can further contain a structural unit represented by the following formula (6) composed of two structural units represented by formula (1-1). By containing this structural unit, the sensitivity can be further improved.

[0122] [Chemical formula]

[0123] In formula (6), Z, X, and Q have the same meanings as in formula (1-1) and formula (1-4). A plurality of Zs, a plurality of Qs, and a plurality of Xs may be the same or different from each other.

[0124] When the polymer P(I) contains a structural unit represented by formula (6), the proportion of the structural unit represented by formula (6) in all the structural units of the polymer P(I) is preferably 1 to 10 mol%, more preferably 1 to 8 mol%.

[0125] In addition to the above structural unit, the polymer P(I) of the present embodiment may contain a structural unit represented by formula (MA). The structural unit represented by formula (MA) is ring-opened by an alkali developer to generate two carboxyl groups. Therefore, the polymer P(I) has excellent developability. When the polymer P(I) contains a structural unit represented by formula (MA), the structural unit represented by formula (MA) in all the structural units of the polymer P(I) is preferably 3 to 40 mol%, more preferably 10 to 30 mol%.

[0126] [Chemical formula]

[0127] In formula (MA), R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0128] The weight average molecular weight Mw of the polymer P(I) is, for example, 2,000 to 50,000. The weight average molecular weight Mw of the polymer P(I) is preferably 2,500 to 45,000, more preferably 3,000 to 40,000. By appropriately adjusting the weight average molecular weight, the sensitivity and the solubility in an alkali developer can be adjusted. Also, the dispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of the polymer P(I) in this embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. By appropriately adjusting the dispersity, the physical properties of the polymer P can be made homogeneous, which is preferable. These values can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0129] The glass transition temperature of the polymer P(I) is preferably 0 to 100°C, more preferably 0 to 80°C. When mainly including the structural unit of formula (NB), the structural unit of formula (ST), the structural unit of formula (IN), or the structural unit of formula (MI), the glass transition temperature tends to be high. On the other hand, when including the structural unit of formula (AK), the structural unit of formula (CA), or the structural unit represented by formula (AD), the glass transition temperature tends to be low. The polymer P in this embodiment has a preferable glass transition temperature by including a structure with a tendency for the glass transition temperature to be high and a structure with a tendency for the glass transition temperature to be low. This is preferable in terms of the pattern formed on the substrate being able to exist stably in the manufacture of liquid crystal display devices and solid-state imaging devices. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0130] The acid value of the polymer P(I) is 70 mgKOH / g or more and 150 mgKOH / g or less, preferably 80 mgKOH / g or more and 140 mgKOH / g or less. Also, the double bond equivalent of the polymer P1 is 100 g / mol or more and 900 g / mol or less, preferably 200 g / mol or more and 850 g / mol or less, more preferably 200 g / mol or more and 800 g / mol or less. When the acid value of the polymer P(I) is 70 mgKOH / g or more, good developability can be obtained. Also, when the double bond equivalent is 900 g / mol or less, the sensitivity of the photosensitive resin composition containing the polymer P(I) can be increased.

[0131] Incidentally, if the acid value of the polymer P(I) is too large, there is a concern that during development with an alkaline developer, the exposed portion may be easily dissolved, resulting in an increase in the exposure amount required for photocuring or an insufficient pattern shape. Therefore, in this embodiment, the upper limit value of the acid value is set to 150 mgKOH / g. On the other hand, if the double bond equivalent of the polymer P(I) is too small (i.e., if the density of double bonds in the polymer is too large), during development with an alkaline developer, unexposed or low-exposure portions tend to be less soluble, and residual films are likely to occur during development. Also, if the double bond equivalent is too small, there is a concern that the molecular weight may increase excessively due to crosslinking, leading to an excessive decrease in solubility. Therefore, in this embodiment, the lower limit value of the double bond equivalent is set to 100 g / mol.

[0132] By having the above configuration, the polymer P(I) of this embodiment can have an alkali dissolution rate of 50 nm / s or more, preferably 100 nm / s or more, more preferably 200 nm / s or more, and particularly preferably 500 nm / s or more. The upper limit value is not particularly limited, but for example, it can be 3000 nm / s or less. If the alkali dissolution rate is too fast, the pattern after development may not have the intended shape. In the present specification, the alkali dissolution rate is the value measured under the following conditions. (Method for measuring alkali dissolution rate) Dissolve the polymer P(I) in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid content concentration of 30% by mass. Next, spin-coat the obtained polymer solution onto a wafer, dry the PGMEA, and perform a pre-bake at a temperature of 100 °C for 2 minutes to produce a resin film with a film thickness of 2 μm ± 0.2. Immerse this resin film, together with the wafer, in a 2.0% by mass aqueous sodium carbonate solution at a temperature of 23 °C. Observe the immersed wafer visually and measure the time until the resin film dissolves and the interference pattern disappears. Divide the film thickness before immersion (2 μm ± 0.2) by that time to calculate the alkali dissolution rate (μm / second).

[0133] By adjusting the acid value and / or double bond equivalent of polymer P(I), it is possible to achieve both higher sensitivity and developability at a higher level.

[0134] The acid value and double bond equivalent of polymer P(I) can be determined by spectral measurement or the like. For example, they can be determined by the following procedure (more specifically, refer to the examples). (1) From the 1 H-NMR chart, determine the area (integral value) of the peaks corresponding to the hydrogen atoms of the carboxy group and the hydrogen atoms near the polymerizable carbon-carbon double bond. (2) From the area determined in (1) and the area of the peak derived from the standard substance, determine the amount of the carboxy group and the amount of the carbon-carbon double bond. (3) Convert the amount of the carboxy group determined in (2) to the acid value (mgKOH / g). Also, convert the amount of the polymerizable carbon-carbon double bond determined in (2) to the double bond equivalent (g / mol).

[0135] The acid value and double bond equivalent of polymer P(I) can be adjusted to desired values by appropriately designing the ratio of the structural units introduced into polymer P(I), particularly the number of polymerizable carbon-carbon double bonds possessed by the (meth)acryloyl group contained in the structural unit represented by formula (1) or formula (2).

[0136] The content (ratio) of each structural unit contained in the polymer P(I) of this embodiment can be estimated / calculated from the charged amount (molar amount) of the raw materials during polymer synthesis, the amount of the remaining raw materials after synthesis, the peak areas of various spectra (for example, 1 the peak area of H-NMR), etc.

[0137] By appropriately selecting the above structural units, the polymer P(I) of the present embodiment has a low softening point of 0°C or higher and 100°C or lower. The softening point of the polymer P(I) is preferably 80°C or lower, more preferably 60°C or lower. Further, the polymer P(I) of the present embodiment has a low melting point of 130°C or lower. The melting point of the polymer P(I) is preferably 110°C or lower, more preferably 90°C or lower. In the present specification, the softening point and melting point of the polymer are the values measured under the following conditions. (Method for measuring softening point) 0.1 to 1.0 mg of the polymer to be measured was placed in an aluminum sample pan, and the softening point was measured using a differential thermal analyzer (manufactured by Hitachi High-Tech Science Corporation, "EXSTAR TMA / SS6100") under a nitrogen atmosphere. The measurement mode was compression, the load was 30 mN, and the temperature was raised at a rate of 3°C / min in the range of 30°C to 200°C. When the sample softened due to heating, the sample deformed and was detected as the displacement amount (μm). The intersection of the extension of the straight line portion without displacement on the low-temperature side or the tangent of the minimum portion of the displacement rate and the tangent of the maximum portion of the displacement rate was defined as the softening point. (Method for measuring melting point) 1 to 2 mg of the polymer to be measured was placed in an aluminum sample pan, and the temperature was raised at a rate of 10°C / min from 30°C while observing the image using a differential thermal analyzer (manufactured by Hitachi High-Technologies Corporation, "STA7200RV") under a nitrogen atmosphere. The temperature at which the melting of the sample started was visually confirmed and defined as the melting point.

[0138] (Method for producing polymer P(I)) The polymer P(I) can be produced (synthesized) by any method. Typically, the polymer P(I) can be produced by the following steps aI, aII, and aIII. In the following description of the method for producing the polymer P(I), as a representative example, the case where the resulting polymer P(I) is a polymer containing a structural unit represented by formula (NB); a structural unit represented by formula (1-2) and / or a structural unit represented by formula (1-3); and a structural unit represented by formula (AD) will be described. Based on the target structure of the polymer P(I), the raw material monomers can be selected.

[0139] When the polymer P(I) contains a structural unit represented by formula (ST) instead of, or in addition to, the structural unit represented by formula (NB), in the following step aI, a raw material monomer represented by formula (STm) may be used instead of, or in addition to, the monomer represented by formula (NBm). Similarly, when the polymer P(I) contains a structural unit represented by formula (IN), in the following step aI, a raw material monomer represented by formula (INm) may be used. When the polymer (I) contains a structural unit represented by formula (AK), in the following step aI, a raw material monomer represented by formula (AKm) may be used. When the polymer (I) contains a structural unit represented by formula (CA), in the following step aI, a raw material monomer represented by formula (CAm) may be used.

[0140] Also, when the polymer P(I) contains a structural unit represented by formula (MI) instead of, or in addition to, the structural unit represented by formula (AD), in step aI, a raw material monomer represented by formula (MIm) may be used instead of, or in addition to, the monomer represented by formula (ADm). When the polymer P(I) contains neither the structural unit represented by formula (AD) nor the structural unit represented by formula (MI), in step aI, neither the monomer represented by formula (ADm) nor the monomer represented by formula (MIm) is used.

[0141] Step aI: Preparing a raw material polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), and a structural unit represented by formula (MA); Step aII: Reacting the raw material polymer obtained in Step aI with a compound having a hydroxy group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound) and / or a compound having a hydroxy group and one (meth)acryloyl group (monofunctional (meth)acrylic compound) in the presence of a basic catalyst to prepare a polymer P(I) (which may be referred to as "polymer precursor (Ia)") containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further containing a structural unit represented by formula (MA). Here, the structural unit represented by formula (1) includes the structure of formula (1-2), and the structural unit represented by formula (2) is a structural unit including the structure of formula (1-3).

[0142] In Step aII, when both the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound are used, it is preferable to first react the polyfunctional (meth)acrylic compound with the raw material polymer obtained in Step aI, and then react the monofunctional (meth)acrylic compound with the resulting reaction mixture.

[0143] When the polymer P(I) further contains a structural unit represented by formula (3), the following Step aIII-i is carried out. Step aIII-i: Treating the polymer precursor (Ia) (corresponding to the polymer P(I) in Step aII above) containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA) obtained in Step aII with water in the presence of a base catalyst to obtain a polymer P(I) (which may be referred to as "polymer precursor (Ib)") containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), a structural unit represented by formula (3), and a structural unit represented by formula (MA).

[0144] When the polymer P(I) further contains a structural unit represented by the formula (1-1), the following step aIII-ii is carried out. Step aIII-ii: A polymer precursor (Ia) (corresponding to the polymer P(I) in the above step aII) containing a structural unit represented by the formula (NB), a structural unit represented by the formula (AD), a structural unit represented by the formula (1) and / or a structural unit represented by the formula (2), and a structural unit represented by the formula (MA) obtained in step aII is reacted with an epoxy group-containing (meth)acrylic compound to prepare a polymer P(I) containing a structural unit represented by the formula (NB), a structural unit represented by the formula (AD), a structural unit represented by the formula (1) and / or a structural unit represented by the formula (2), a structural unit represented by the formula (1-1), and a structural unit represented by the formula (MA).

[0145] Either step aIII-i or step aIII-ii may be carried out. When both are carried out, it is preferable to carry out step aIII-ii after step aIII-i. The polymer P(I) obtained via steps aII and aIII-ii without going through step aIII-i may contain a structural unit represented by the formula (8) and / or a structural unit represented by the formula (9). When steps aII, aIII-i, and aIII-ii are carried out, in step aIII-ii, the polymer precursor (Ib) obtained in step aIII-i is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P(I) which may contain a structural unit represented by the formula (8) and / or a structural unit represented by the formula (9), a structural unit represented by the formula (5), and a structural unit represented by the formula (6).

[0146] Hereinafter, each step will be described. (Step aI) In Project aI, the step of preparing a raw material polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), and a structural unit represented by formula (MA) can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (NBm), a monomer represented by formula (ADm), and a monomer represented by formula (MAm). Here, R 1 in formula (NBm), R 2 in formula (NBm), R 3 in formula (NBm), and R 4 in formula (NBm) as well as the definition of a1 are the same as those in formula (NB). Also, R 11 in formula (ADm), R 12 in formula (ADm), R 13 in formula (ADm), and R 14 in formula (ADm) have the same definition as those in formula (AD). Further, the definition of R 21 and R 22 in formula (MAm is the same as that in formula (MA). In addition, when the polymer P(I) contains a structural unit represented by formula (ST), a structural unit represented by formula (IN), a structural unit represented by formula (AK), and / or a structural unit represented by formula (CA), a monomer represented by formula (STm), a monomer represented by formula (INm), a monomer represented by formula (AKm), and / or a monomer represented by formula (CAm) is used respectively. The definition of the substituents of each monomer is the same as that in the corresponding structural unit. Also, when the polymer P(I) contains a structural unit represented by formula (MI), a raw material monomer represented by formula (IMm) is used. Here, the definition of the substituents in formula (MIm) is the same as that in formula (MI).

[0147] (Monomer represented by formula (NBm))

Chemical Formula

[0148] Examples of the monomer represented by formula (NBm) include norbornene, bicyclo[2.2.1]hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, 5-norbornene-2,3-dicarboxylic anhydride, and the like. When polymerizing, only one type of the monomer represented by formula (NBm) may be used, or two or more types may be used in combination.

[0149] (Monomer represented by formula (STm))

Chemical formula

[0150] (Monomer represented by formula (INm))

Chemical formula

[0151] (Monomer represented by formula (AKm))

Chemical formula

[0152] In the long-chain alkene as the monomer represented by the formula (AKm), the configuration around the double bond may be either cis-type or trans-type. Examples of the long-chain alkene represented by the formula (AKm) include linear 1-alkenes such as 1-hexene, 1-heptadecene, 1-octene, 1-decene, 1-undecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-tricosene; branched-chain 1-alkenes such as 3,5,5-trimethyl-1-hexene; linear or branched-chain alkenes such as 4-octene, 3-octene, 2-decene, 5-methyl-2-heptene, 5-methyl-3-heptene, 2,4,4-trimethyl-2-pentene, 3-methyl 2-heptene, cis-9-tricosene.

[0153] (Monomer represented by the formula (CAm))

Chemical formula

[0154] In the carboxylic acid-containing alkene as the monomer represented by the formula (CAm), the configuration around the double bond may be either cis-type or trans-type. Examples of the carboxylic acid-containing alkene represented by the formula (CAm) include linear carboxylic acid-containing alkenes having a terminal double bond such as 3-butenoic acid, 4-pentenoic acid, 7-octenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 22-tricosenoic acid; linear carboxylic acid-containing alkenes such as 3-hexenoic acid, 2-pentenoic acid, 3-pentenoic acid, 4-methyl-2-pentenoic acid, 13-docosenoic acid, oleic acid; branched-chain carboxylic acid-containing alkenes having a terminal double bond such as 2-methyl-4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid.

[0155] (Monomer represented by the formula (ADm))

Chemical formula

[0156] In the unsaturated dicarboxylic acid dialkyl ester as the monomer represented by the formula (ADm), the configuration around the double bond may be either cis or trans, and it may be either a monomer represented by the formula (t-ADm) which is trans or a monomer represented by the formula (c-ADm) which is cis. Specific examples of the monomer represented by the formula (t-ADm) include dibutyl fumarate, diethyl fumarate, bis(2-ethylhexyl) fumarate, dimethyl fumarate, etc. Examples of the monomer represented by the formula (c-ADm) include dibutyl maleate, diethyl maleate, bis(2-ethylhexyl) maleate, dimethyl maleate, etc.

[0157] (Monomer represented by formula (t-ADm)) [Chemical formula]

[0158] (Monomer represented by formula (c-ADm)) [Chemical formula]

[0159] (Monomer represented by formula (MIm)) [Chemical formula]

[0160] (Monomer represented by formula (MAm)) [Chemical formula]

[0161] The polymerization method is not limited, but radical polymerization using a radical polymerization initiator is preferred. As the radical polymerization initiator, for example, azo compounds, organic peroxides, etc. can be used. Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), 1,1'-azobis(cyclohexanecarbonitrile) (ABCN), and the like. Examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Regarding the polymerization initiator, only one kind may be used, or two or more kinds may be used in combination.

[0162] As the solvent used in the polymerization reaction, for example, organic solvents such as diethyl ether, tetrahydrofuran, toluene, and methyl ethyl ketone can be used. The polymerization solvent may be a single solvent or a mixed solvent.

[0163] The synthesis of the raw material polymer is carried out by dissolving the monomer represented by the formula (NBm), the monomer represented by the formula (ADm), the monomer represented by the formula (MAm), and the polymerization initiator in a solvent, charging them into a reaction vessel, and then heating to allow the addition polymerization to proceed. The heating temperature is, for example, 50 to 80 °C, and the heating time is, for example, 5 to 20 hours. When charging into the reaction vessel, the molar ratio (ADm + MAm) of the total amount of the monomer represented by the formula (NBm), the monomer represented by the formula (ADm), and the monomer represented by the formula (MAm) is preferably (NBm):(ADm + MAm) = 0.5:1 to 1:0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 0.5:0.8 to 0.7:0.5. The molar ratio of the monomer represented by the formula (ADm) and the monomer represented by the formula (MAm) is preferably (ADm):(MAm) = 0.5:9.5 to 8:2, and more preferably 1:9 to 7:4.

[0164] When the raw material polymer of interest contains a structural unit represented by formula (AD) and / or a structural unit represented by formula (MI); a structural unit represented by formula (MA); and at least one structural unit selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), a structural unit represented by formula (IN), a structural unit represented by formula (AK), and a structural unit represented by formula (CA), it is preferably used in an amount such that the mixed molar ratio of each monomer is (NBm + STm + INm + AKm + CAm):(ADm + MAm + MIm) = 0.5:1 to 1:0.5, and it is particularly preferred from the viewpoint of controlling the molecular structure of the polymer to use it in an amount such that (NBm + STm + INm + AKm + CAm):(ADm + MAm + MIm) = 0.5:0.8 to 0.7:0.5.

[0165] The raw material polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, etc. Typically, it is a random copolymer or an alternating copolymer. Incidentally, maleic anhydride is generally known as a monomer with strong alternating copolymerizability.

[0166] After the synthesis of the raw material polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be performed. Specifically, the organic phase containing the synthesized raw material polymer and low molecular weight components is concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. Then, this solution is mixed with a poor solvent such as methanol, 2-propanol, 1-butanol, etc. to precipitate the monomer. By filtering and drying this precipitate, the purity of the raw material polymer can be increased.

[0167] (Step aII) In Step aII, the raw material polymer obtained in Step aI is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst, so that a part of the structural unit represented by formula (MA) contained in the raw material polymer undergoes ring opening, and a structural unit represented by formula (1) and / or a structural unit represented by formula (2) are formed, to obtain a polymer precursor containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally containing a structural unit represented by formula (MA). The polymer precursor obtained here can be used as the polymer P(I) of the present embodiment, but for the sake of convenience of explanation, it is referred to as "polymer precursor (Ia)".

[0168] More specifically, first, a solution in which the raw material polymer is dissolved in an appropriate organic solvent is prepared. As the organic solvent, a single solvent or a mixed solvent such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF) can be used, but it is not limited to these, and various organic solvents used in the synthesis of organic compounds and polymers can be used.

[0169] When obtaining a polymer precursor containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), and both a structural unit represented by formula (1) and a structural unit represented by formula (2), next, a polyfunctional (meth)acrylic compound is added to the above solution. Further, a basic catalyst is added. Then, the solution is appropriately mixed to form a uniform solution, and a polymer precursor (Ia') containing at least a structural unit of formula (NB), a structural unit of formula (AD), and a structural unit of formula (1) is obtained (Step aII-i).

[0170] Examples of the polyfunctional (meth)acrylic compound that can be used here include a compound represented by formula (1b-m), a compound represented by formula (1c-m), and a compound represented by formula (1d-m). k, R, X in formula (1b-m) 1 、X1 ' and X 2 The definitions and specific embodiments of are the same as those in the above formula (1b). Also, k, R, X in the formulas (1c-m) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definitions and specific embodiments of are the same as those in the above formula (1c). n and R in the formulas (1d-m) are the same as those in the above formula (1d).

[0171]

Chemical formula

[0172]

Chemical formula

[0173]

Chemical formula

[0174] Next, a polymer precursor (Ia) containing a structural unit of formula (NB), a structural unit of formula (AD), a structural unit of formula (1), and a structural unit of formula (2) can be obtained by reacting the polymer precursor (Ia') obtained in step aII-i with a monofunctional (meth)acrylic compound in the presence of a basic catalyst (step aII-ii).

[0175] As the basic catalyst, amine compounds, nitrogen-containing heterocyclic compounds, etc. known in the field of organic synthesis can be appropriately used. For example, amine compounds or nitrogen-containing heterocyclic compounds such as triethylamine, pyridine, and dimethylaminopyridine can be used as the catalyst. The usage amount of the basic catalyst can be, for example, about 10 to 60 parts by mass with respect to 100 parts by mass of the raw material polymer. It should be noted that if the basic catalyst is used in excess, the amount of acid required for neutralization will increase, and there is a possibility that purification will become complicated.

[0176] The above solution is preferably heated at 60 to 80 °C for about 3 to 9 hours, whereby ring-opening of the structural unit of formula (MA) contained in the raw material polymer / formation of the structural unit of formula (1) is carried out.

[0177] For example, during the above heating, by adding a monofunctional (meth)acrylic compound having a hydroxy group to the reaction system, ring-opening of the structural unit of formula (MA) contained in the raw material polymer / formation of the structural unit of formula (2) is carried out, and a polymer precursor (Ia) having the structural unit represented by formula (2) is generated.

[0178] From the viewpoint of steric hindrance of the reaction, a monofunctional (meth)acrylic compound having a hydroxy group tends to react more easily with the raw material polymer than a polyfunctional (meth)acrylic compound having a hydroxy group. Therefore, when preparing a polymer precursor having the structural unit of formula (2), it is preferable not to initially charge a monofunctional (meth)acrylic compound having a hydroxy group into the reaction system but to add it to the reaction system. Examples of the monofunctional (meth)acrylic compound having a hydroxy group include compounds represented by the following formulae (2a-m). In formulae (2a-m), X 10 and the definitions of R are the same as those in formula (2a).

[0179]

Chemical formula

[0180] Specific examples of the compounds represented by formulae (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, and the like.

[0181] When obtaining a polymer precursor (Ia) containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), and either one of the structural unit represented by formula (1) and the structural unit represented by formula (2), only one of step aII-i and step aII-ii may be carried out after step (I).

[0182] (Step aIII-i) When carrying out step aIII-i, a step of treating the polymer precursor (Ia) obtained in step aII with water in the presence of a basic catalyst is used. By step aIII-i, the structural unit represented by formula (MA) contained in the polymer precursor (Ia) obtained in step aII undergoes ring-opening to form a structural unit represented by formula (3), and a polymer P(I) containing a structural unit represented by formula (NB); a structural unit represented by formula (AD); a structural unit represented by formula (1) and / or a structural unit represented by formula (2); and a structural unit represented by formula (3) (hereinafter, may be referred to as "polymer precursor (Ib)") can be produced. When a part of the structural unit represented by formula (MA) undergoes ring-opening and a part of the structural unit of formula (MA) remains without undergoing ring-opening, the polymer P(I) further contains a structural unit represented by formula (MA).

[0183] Examples of the basic catalyst used in step aIII-i include amine compounds or nitrogen-containing heterocyclic compounds such as triethylamine, pyridine, and dimethylaminopyridine.

[0184] In step aIII-i, water is added to the reaction system containing the polymer precursor (Ia) obtained in step aII, and the resulting reaction solution is heated, preferably at 60 to 80 °C for about 0.25 to 6 hours, so that the structural unit of formula (MA) contained in this polymer undergoes ring-opening to generate a structural unit represented by formula (3). The basic catalyst can be used as it is the catalyst remaining in the reaction system obtained in step aII. Therefore, step aIII-i is preferably carried out by adding water to this reaction mixture in situ without performing any post-treatment on the reaction mixture obtained in step aII.

[0185] Through the above steps, the polymer P(I) (polymer precursor (Ia) or polymer precursor (Ib)) of the present embodiment can be obtained. However, from the perspective of the effects of the present invention, in order to remove unnecessary components other than the desired polymer, the following steps can be further appropriately performed.

[0186] First, the reaction solution diluted with an organic solvent and added with an acid (such as formic acid) above is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more to separate into an organic phase and an aqueous phase, and the aqueous phase is removed. In this way, an organic solution of the polymer P(I) (polymer precursor (Ia) or polymer precursor (Ib)) is obtained.

[0187] The obtained organic solution of the polymer P(I) (polymer precursor (Ia) or polymer precursor (Ib)) is purified using a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the obtained organic solution of P(I) (polymer precursor (Ia) or polymer precursor (Ib)) is added to an excessive amount of toluene or water to reprecipitate the polymer. Further, the polymer powder obtained by reprecipitation is washed several times with toluene or water. Furthermore, in order to remove formic acid and the basic catalyst, the operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (about 1 to 3 times). By drying the polymer powder after washing with ion-exchanged water at, for example, 30 to 60 °C for 16 hours or more, a high-purity polymer can be obtained. In the liquid-liquid extraction method, water or a mixed solution of water and an alcohol such as methanol, 2-propanol, or 1-butanol is added to the obtained organic solution of the polymer P(I), and it is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more to separate into an organic phase and an aqueous phase, and the aqueous phase is removed. Further, water or a mixed solution of water and an alcohol is added to the organic solution of the polymer after removing the aqueous phase, and it is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more to separate into an organic phase and an aqueous phase, and the aqueous phase is removed. In this way, an organic solution of the polymer is obtained. If necessary, the steps of adding water or a mixed solution of water and an alcohol and removing the aqueous phase may be further performed. By heating the obtained organic solution of polymer P(I) under reduced pressure using a rotary evaporator, concentrating it, and then repeating the operation of adding and diluting with the final solvent (such as PGMEA), a polymer solution dissolved in the final solvent can be obtained. Additionally, purification may be further performed by reprecipitation after solvent substitution.

[0188] Also, the polymer solution may contain a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound used when synthesizing polymer P(I). When the polymer solution contains these (meth)acrylic compounds, the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart is preferably in an amount of 0.25 to 50%, particularly 0.5 to 30%, based on the peak area of polymer P, and the peak area derived from the monofunctional (meth)acrylic compound is preferably in an amount of 0.25 to 50%, particularly 0.5 to 30%, based on the peak area of polymer P. Thereby, the photosensitive resin composition containing this polymer solution has good alkali solubility and good sensitivity in photolithography.

[0189] (Step aIII-ii) In step aIII-ii, the polymer (polymer precursor (Ia)) obtained in step aII or the polymer (polymer precursor (Ib)) obtained in step aIII-i is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst, so that the carboxyl group of polymer precursor (Ia) or (Ib) reacts with the epoxy group of the epoxy group-containing (meth)acrylic compound, forming a structural unit represented by formula (1-1), and a structural unit represented by formula (NB); a structural unit represented by formula (AD); a structural unit represented by formula (1) and / or a structural unit represented by formula (2); and polymer P(I) containing a structural unit represented by formula (1-1) can be produced. When a part of the structural unit represented by formula (MA) is ring-opened and a part of the structural unit of formula (MA) remains without ring-opening, polymer P(I) further contains a structural unit represented by formula (MA).

[0190] Step aIII-ii is preferably carried out by adding an epoxy group-containing (meth)acrylic compound to a reaction system containing the polymer precursor (Ib) obtained in step aIII-i.

[0191] The reaction between the polymer precursor (Ia) or (Ib) and the epoxy group-containing (meth)acrylic compound proceeds in the presence of a basic catalyst. The basic catalyst can be directly used as the catalyst remaining in the reaction system obtained in step aII. Therefore, step aIII-ii can be carried out in situ, without isolating and purifying the polymer precursor (Ia) from the reaction mixture containing the polymer precursor (Ia) obtained in step aII, or without isolating and purifying the polymer precursor (Ib) from the reaction mixture containing the polymer precursor (Ib) obtained in step aIII-i, or without neutralizing the basic catalyst contained in the mixture, by adding an epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor (Ia) obtained in step aII, or to the reaction mixture containing the polymer precursor (Ib) obtained in step aIII-i.

[0192] Specifically, by heating the reaction solution obtained by adding an epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor (Ia) or (Ib) at preferably 60 to 80°C for about 1 to 9 hours, the reaction between the carboxyl group of the polymer precursor (Ia) or (Ib) and the epoxy group of the epoxy group-containing (meth)acrylic compound forms the structural unit represented by formula (1-1), and the polymer P(I) is produced.

[0193] Examples of the epoxy group-containing (meth)acrylic compound include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, glycidyl acrylate, etc., and one or more selected therefrom can be used.

[0194] The addition amount of the epoxy group-containing (meth)acrylic compound is desirably 0.1 to 3.0 moles per mole of the carboxyl group of the polymer precursor (Ia) or (Ib).

[0195] When the polymer P(I) is a polymer obtained via the polymer precursor (Ia), the polymer P(I) includes a structural unit represented by formula (NB); a structural unit represented by formula (AD); a structural unit represented by formula (8); a structural unit represented by formula (9); a structural unit represented by formula (1); and a structural unit represented by formula (2).

[0196] When the polymer P(I) is a polymer obtained via the polymer precursor (Ib), the polymer P(I) includes a structural unit represented by formula (NB); a structural unit represented by formula (AD); a structural unit represented by formula (8); a structural unit represented by formula (9); a structural unit represented by formula (5); a structural unit represented by formula (6); a structural unit represented by formula (1); a structural unit represented by formula (2); a structural unit represented by formula (3); and a structural unit represented by formula (MA).

[0197] After step aIII-ii, it is preferable to appropriately perform the following steps as necessary for removing unnecessary components other than the desired polymer P(I).

[0198] First, the reaction solution diluted with an organic solvent and added with an acid (e.g., formic acid, citric acid, etc.) is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more to separate into an organic phase and an aqueous phase, and the aqueous phase is removed. Thus, an organic solution of the polymer P(I) is obtained.

[0199] An excessive amount of toluene is added to the obtained organic solution of the polymer P(I) to reprecipitate the polymer P(I). Further, the polymer powder obtained by reprecipitation is washed with toluene several times (e.g., 2 times). Furthermore, for removing the acid and the basic catalyst, the operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (e.g., 3 times). The polymer powder after washing with ion-exchanged water can be dried, for example, at 30 to 60 °C for 16 hours or more to obtain the high-purity polymer P(I) of the present embodiment.

[0200] <Second Embodiment> (Polymer P(II)) The polymer P (hereinafter referred to as "polymer P(II)") in the second embodiment contains at least one structural unit selected from the structural unit represented by the formula (1-2) and the structural unit represented by the above formula (1-3), and has a structure represented by the formula (P1). In the polymer P(II), in the formula (P1), a polymer chain typically containing a structural unit B is bonded to a monofunctional or polyfunctional thiol group-containing compound-derived C1-C30 monovalent to hexavalent organic group represented as "Y". The C1-C30 monovalent to hexavalent organic group derived from this monofunctional or polyfunctional thiol group-containing compound is typically a C1-C30 organic group containing 1 to 6 thioether groups.

[0201]

Chemical formula

[0202] In the formula (P1), n is an integer of 1 to 6, X is hydrogen or a C1-C30 organic group, Y is a monovalent to hexavalent C1-C30 organic group derived from a monofunctional or polyfunctional thiol group-containing compound, B contains at least one structural unit selected from the structural unit represented by the formula (1-2) and the structural unit represented by the above formula (1-3), A plurality of Bs may be the same or different from each other.

[0203] In one embodiment, the polymer P(II) may further include at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), the structural unit represented by formula (IN), the structural unit represented by formula (AK), and the structural unit represented by formula (CA). In that case, it has the structure represented by formula (P2).

[0204]

Chemical formula

[0205] In formula (P2), n is an integer from 1 to 6, p and q represent the molar contents of structural units A and B contained in each polymer chain within n [ ]. p and q may be the same or different for each polymer chain within n [ ]. p + q = 1, p is 0 or more, and q is 0 or more. Regarding the molar contents of each structural unit A and B contained in the polymer as p t and q t respectively, then p t + q t = 1. p t is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, and even more preferably 0.35 to 0.6. q t is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, and even more preferably 0.35 to 0.6. X is hydrogen or an organic group having 1 to 30 carbon atoms. Y is a monofunctional or polyfunctional organic group having 1 to 6 valences and 1 to 30 carbon atoms derived from a thiol group-containing compound. A represents at least one structural unit selected from the structural unit represented by the above formula (NB), the structural unit represented by the above formula (ST), the structural unit represented by the above formula (IN), the structural unit represented by the above formula (AK), and the structural unit represented by the above formula (CA). B contains at least one structural unit selected from the structural unit represented by the above formula (1-2) and the structural unit represented by the above formula (1-3), A plurality of A's and a plurality of B's may be the same or different from each other.

[0206] In one embodiment, the polymer P(II) may further contain at least one structural unit selected from the structural unit represented by the formula (MI) and the structural unit represented by the above formula (AD), and in that case, it has the structure represented by the formula (P3).

[0207]

Chemical formula

[0208] In the formula (P3), n is an integer from 1 to 6, p, q, and r represent the molar contents of the structural units A, B, and C contained in each polymer chain within n [ ], p, q, and r may be the same or different for each polymer chain within n [ ], p + q + r = 1, p is 0 or more, q is 0 or more, and r is 0 or more, Regarding the molar contents of the respective structural units A, B, and C contained in the polymer, let them be p t , q t , and r t respectively. Then, p t + q t + r t = 1, p t is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, and even more preferably 0.35 to 0.60, q t is greater than 0, preferably 0.10 to 0.6, more preferably 0.2 to 0.50, and even more preferably 0.25 to 0.45, r tis greater than 0, preferably from 0.03 to 0.3, more preferably from 0.04 to 0.28, and particularly preferably from 0.05 to 0.25. X is hydrogen or an organic group having 1 to 30 carbon atoms. Y is a monofunctional or polyfunctional thiol group-containing compound-derived organic group having 1 to 30 carbon atoms and 1 to 6 valences. A represents at least one structural unit selected from the structural unit represented by the above formula (NB), the structural unit represented by the above formula (ST), the structural unit represented by the above formula (IN), the structural unit represented by the above formula (AK), and the structural unit represented by the above formula (CA). B contains at least one structural unit selected from the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3). C represents the structural unit represented by formula (AD) and the structural unit represented by the above formula (MI). A plurality of As, Bs, and Cs may be the same or different from each other.

[0209] The polymer P(II) represented by formula (P1), formula (P2), or formula (P3) may contain the structural unit represented by the above formula (1-1) as the structural unit B. The polymer P(II) represented by formula (P1), formula (P2), or formula (P3) may contain the structural unit represented by the above formula (1-4) as the structural unit B. The polymer P(II) represented by formula (P1), formula (P2), or formula (P3) may contain at least one selected from the structural unit represented by the above formula (1) and the structural unit represented by formula (2) as the structural unit B. The polymer P(II) represented by formula (P1), formula (P2), or formula (P3) may contain the structural unit represented by the above formula (3) as the structural unit B. The polymer P(II) represented by formula (P1), formula (P2), or formula (P3) may contain at least one selected from the structural unit represented by the above formula (8) and the structural unit represented by formula (9) as the structural unit B. The polymer P(II) represented by formula (P1), formula (P2) or formula (P3) may contain, as structural unit B, the structural unit represented by the above formula (5). The polymer P(II) represented by formula (P1), formula (P2) or formula (P3) may contain, as structural unit B, the structural unit represented by the above formula (6). The polymer P(II) represented by formula (P1), formula (P2) or formula (P3) may contain, as structural unit B, the structural unit represented by the above formula (MA).

[0210] In formula (P3), X is hydrogen or an organic group having 1 to 30 carbon atoms. The organic group having 1 to 30 carbon atoms is the same as the organic group having 1 to 30 carbon atoms that can constitute R in the above formula (ST). 43

[0211] In formula (P1), formula (P2) or formula (P3), Y is a monofunctional or polyfunctional (bifunctional or higher) organic group having 1 to 30 carbon atoms derived from a thiol group-containing compound (referred to as "organic group (i)" in this specification). In this embodiment, the valence number is the number of functional groups (the number of thiol groups). That is, the monofunctional or polyfunctional thiol group-containing compound contains one or more thiol groups, and organic group (i) is bonded to the structural units within [ ]n and the structural units within [ ]m via 1 to 6 thioether groups derived from the thiol group. Organic group (i) may have a thiol group that does not participate in the bonding with the structural units within [ ]n and the structural units within [ ]m, and polymer P(II) can be obtained as a mixture of respective resins where the number (number of bonds) of (n + m) is 1 to 6. The organic group (i) having 1 to 30 carbon atoms is monofunctional or polyfunctional (bifunctional or higher), preferably polyfunctional (bifunctional or higher), more preferably trifunctional or higher. The upper limit value is not particularly limited, but it is hexafunctional or less. From the viewpoint of the effects of the present invention, the valence number of the organic group (i) having 1 to 30 carbon atoms is, for example, 1 to 6, preferably 2 to 6, more preferably 3 to 6.

[0212] ​The monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms may contain one or more atoms selected from O, N, S, P, and Si. Examples of the monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, an alkoxy group, and a heterocyclic group having 1 to 6 thioether groups (-S-*(* is a bond)).

[0213] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.

[0214] Examples of the alkynyl group include an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group.

[0215] Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

[0216] Examples of the monofunctional or polyfunctional thiol group-containing compounds that can introduce Y in formula (P1), formula (P2), or formula (P3) include compounds represented by the following chemical formulas (s-1) to (s-21). That is, polymer P(II) contains a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound represented by the following.

[0217]

Chem.

[0218]

Chem.

[0219]

Chem.

[0220]

Chem.

[0221]

Chem.

[0222]

Chem.

[0223]

Chem.

[0224]

Chem.

[0225]

Chem.

[0226]

Chem.

[0227]

Chem.

[0228]

Chem.

[0229]

Chem.

[0230]

Chem.

[0231]

Chem.

[0232]

Chem.

[0233]

Chem.

[0234]

Chem.

[0235]

Chem.

[0236] [Chemistry]

[0237] [Chemistry]

[0238] The monofunctional or polyfunctional thiol group-containing compound may be used alone or in combination of two or more. Among them, it is preferable to use a 3-6 functional (3-6 valent) thiol group-containing compound having 3 to 6 thiol groups in one molecule in terms of excellent reactivity with other monomers. In the present embodiment, the monofunctional or polyfunctional thiol group-containing compound preferably includes compounds represented by the above formulas (s-1) to (s-3), (s-5), and (s-8) to (s-10) among the compounds represented by the above formulas (s-1) to (s-21), and particularly preferably includes compounds represented by the chemical formulas (s-1) to (s-3), (s-5), and (s-9). The monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms has a thioether group (-S-* (* is a bond)) derived from the thiol group of these thiol group-containing compounds at the terminal, and is bonded to the structural unit within [ ]n and the structural unit within [ ]m via the thioether group. The organic group (i) may have a thiol group that does not participate in the bonding with the structural unit within [ ]n and the structural unit within [ ]m.

[0239] When the polymer P(II) of the present embodiment has a structure represented by the formula (P3) and the polymer P(II) is obtained by using the tetrafunctional (tetravalent) thiol group-containing compound represented by the above formula (s-2) as the monofunctional or polyfunctional thiol group-containing compound, the polymer P(II) may have a structure represented by the following formula (I).

[0240] [Chemistry]

[0241] In formula (I), A, B, C, X, p, q, and r are synonymous with those in formula (P3). However, for the purpose of explanation in formula (I), p, q, and r for each of the four polymer chains within the four [ ] are represented as p 1 ~p 4 , q 1 ~q 4 , r 1 ~r 4 as described. In formula (I), p 1 ~p 4 , q 1 ~q 4 , r 1 ~r 4 may be the same or different for each of the four polymer chains within the four [ ], and p 1 +q 1 +r 1 =1, p 2 +q 2 +r 2 =1, p 3 +q 3 +r 3 =1, p 4 +q 4 +r 4 =1. When the molar contents of each of the structural units A, B, and C contained in the polymer represented by formula (I) are p t , q t , and r t respectively, p t =p 1 +p 2 +p 3 +p 4 , q t =q 1 +q 2 +q 3 +q 4 , r t =r 1 +r 2 +r 3 +r 4 That is.

[0242] In formula (I), the bonding order of A, B, and C is not particularly limited, and any of A, B, and C may be bonded to the thioether group. In formula (I), an example is shown in which it is bonded to the four structural units within the [ ] via thioether groups derived from the four mercapto groups of the compound represented by chemical formula (s-2). However, a structure in which 1 to 3 structural units within the [ ] are bonded to the thioether groups derived from the four mercapto groups, and different organic groups from the structural units within the [ ] are bonded to the remaining thioether groups may also be possible. In the present embodiment, the polymer P can be obtained as a mixture containing at least one compound in which 1 to 4 structures within the [ ] are bonded.

[0243] Physical properties such as the weight average molecular weight Mw, dispersity (weight average molecular weight Mw / number average molecular weight Mn), glass transition temperature, softening point, melting point, acid value, double bond equivalent, and alkali dissolution rate of the polymer P(II) are the same as those of the above-described polymer P(I).

[0244] (Method for producing polymer P(II)) The polymer P(II) can be produced (synthesized) by any method. Typically, the polymer P(II) can be produced by the following steps bI, bII, and bIII. In the following description of the method for producing the polymer P(II), for convenience, the case where the resulting polymer P(II) is a polymer containing a structural unit represented by formula (NB); a structural unit represented by formula (1-2) and / or a structural unit represented by formula (1-3); and a structural unit represented by formula (AD) will be described. Based on the target structure of the polymer P(II), the raw material monomers can be selected. Step bI: A step of preparing a raw material polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), a structural unit represented by formula (MA), and a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms; Process bII-i: A step of reacting the raw material polymer obtained in Process bI with a compound having a hydroxy group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound) and / or a compound having a hydroxy group and one (meth)acryloyl group (monofunctional (meth)acrylic compound) in the presence of a basic catalyst to prepare a first polymer precursor (IIa) containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further containing a structural unit represented by formula (MA).

[0245] When the polymer P(II) further contains a structural unit represented by formula (3), the following Process bIII-i is carried out. Process bIII-i: A step of treating the polymer precursor (IIa) (corresponding to the polymer P(II) in the above Process bII) containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA) obtained in Process bII with water in the presence of a base catalyst to obtain a polymer P(II) (which may be referred to as "polymer precursor (IIb)") containing a structural unit represented by formula (NB); a structural unit represented by formula (AD); a structural unit represented by formula (1) and / or a structural unit represented by formula (2); a structural unit represented by formula (3); a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms; and a structural unit represented by formula (MA).

[0246] When the polymer P(II) further contains a structural unit represented by formula (1-1), the following Process bIII-ii is carried out. Step bIII-ii: React the polymer precursor (IIa) obtained in step bII or the polymer precursor (IIb) obtained in step aIII-i with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to obtain at least a structural unit represented by formula (NB); a structural unit represented by formula (AD); a structural unit represented by formula (1) and / or a structural unit represented by formula (2); a structural unit represented by formula (1-1); a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms; and a polymer P(II) containing a structural unit represented by formula (MA).

[0247] Either step bIII-i or step bIII-ii may be carried out. When both are carried out, it is preferable to carry out step bIII-ii after step bIII-i. The polymer P(I) obtained via steps bII and bIII-ii without going through step bIII-i may contain a structural unit represented by formula (8) and / or formula (9). When steps bII, bIII-i, and bIII-ii are carried out, step bIII-ii is a step of reacting the polymer precursor (IIb) obtained in step bIII-i with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P(II) which may contain a structural unit represented by formula (8) and / or formula (9), a structural unit represented by formula (5), and a structural unit represented by formula (6).

[0248] In step bII, when both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used, it is preferable to first react the polyfunctional (meth)acrylic compound with the raw material polymer obtained in step bI, and then react the monofunctional (meth)acrylic compound with the resulting reaction mixture.

[0249] Hereinafter, each step will be described. (Step bI) In Step bI, the step of preparing a raw material polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (AD), a structural unit represented by formula (MA), and a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (NBm), a monomer represented by formula (ADm), and a monomer represented by formula (MAm) in the presence of a monofunctional or polyfunctional thiol group-containing compound.

[0250] Examples of the monofunctional or polyfunctional thiol group-containing compound include, but are not limited to, the compounds represented by the above formulas (s-1) to (s-21). The monofunctional or polyfunctional thiol group-containing compound may be used alone or in combination of two or more. The specific conditions of Step bI are the same as those of Step aI in the method for producing Polymer P(I) of the first embodiment.

[0251] (Step bII) The same conditions as those of Step aII in the method for producing Polymer P(I) of the first embodiment can be applied to Step bII.

[0252] (Step bIII-i) The same conditions as those of Step aIII-i in the method for producing Polymer P(I) of the first embodiment can be applied to Step bIII-i. (Step bIII-i) The same conditions as those of Step aIII-ii in the method for producing Polymer P(I) of the first embodiment can be applied to Step bIII-ii.

[0253] <Third Embodiment> (Polymer P(III)) The polymer P in the third embodiment (hereinafter referred to as "Polymer P(III)") contains a structural unit represented by formula (AD). The softening point of the Polymer P(III) is 60°C or higher and 130°C or lower.

[0254] [Chemical Formula]

[0255] In formula (MA), R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0256] Polymer P(III) is a raw material polymer used in the production of polymer P(I) in the first embodiment and is a polymer obtained in the step of step aI.

[0257] In one embodiment, polymer P(III) may contain at least one structural unit selected from the structural unit represented by the above formula (NB), the structural unit represented by the above formula (ST), the structural unit represented by the above formula (IN), the structural unit represented by the above formula (AK), and the structural unit represented by the above formula (CA).

[0258] In one embodiment, polymer P(III) may contain at least one structural unit selected from the structural unit represented by the above formula (MI) and the structural unit represented by the above formula (AD).

[0259] By containing the above-described structural units, polymer P(III) has a low softening point of 158°C or lower. The softening point of polymer P(III) is preferably 150°C or lower, more preferably 140°C or lower, and even more preferably 130°C or lower. Also, by containing the above-described structural units, polymer P(III) has a low melting point of 180°C or lower. The melting point of polymer P(III) is preferably 170°C or lower, more preferably 160°C or lower, and even more preferably 150°C or lower.

[0260] The weight average molecular weight Mw of polymer P(III) is, for example, from 1,000 to 20,000. The weight average molecular weight Mw of polymer P(III) is preferably from 1,500 to 15,000. By appropriately adjusting the weight average molecular weight, it becomes possible to adjust the weight average molecular weight of polymer P(I) obtained from this polymer P(III), and as a result, the sensitivity of polymer P(III) and the solubility in an alkaline developer can be adjusted to a desired level. Also, the dispersity (weight average molecular weight Mw / number average molecular weight Mn) of polymer P(III) is preferably from 1.0 to 5.0, more preferably from 1.0 to 4.0, still more preferably from 1.0 to 3.0.

[0261] <Fourth Embodiment> (Polymer P(IV)) The polymer in the fourth embodiment of the present invention (referred to as "polymer P(IV)" in this specification) contains a structural unit represented by formula (MA) and has a structure represented by formula (P1'). In polymer P(IV), in formula (P1'), a polymer chain typically containing structural unit B is bonded to a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound represented as "Y". The monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from this monofunctional or polyfunctional thiol group-containing compound is typically an organic group having 1 to 30 carbon atoms containing 1 to 6 thioether groups.

[0262] [Chemical formula]

[0263] In formula (P1'), n is an integer from 1 to 6, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound, B' represents the structural unit represented by the above formula (MA).

[0264] In one embodiment, the polymer P(IV) may further contain at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), the structural unit represented by formula (IN), the structural unit represented by formula (AK), and the structural unit represented by formula (CA), and in that case, it has the structure represented by formula (P2').

[0265]

Chemical formula

[0266] In formula (P2'), n is an integer from 1 to 6, p, q', and r represent the molar contents of structural units A and B' contained in each polymer chain within n [ ], p and q' may be the same or different for each polymer chain within n [ ], p + q' = 1, p is 0 or more, and q' is 0 or more, When the molar contents of each structural unit A and B' contained in the polymer are p t and q t ' respectively, then p t + q t ' = 1, p t is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, and even more preferably 0.35 to 0.6, q t ' is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, and even more preferably 0.35 to 0.6, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound, A represents at least one structural unit selected from the structural unit represented by the above formula (NB), the structural unit represented by the above formula (ST), the structural unit represented by the above formula (IN), the structural unit represented by the above formula (AK), and the structural unit represented by the above formula (CA). B' represents a structural unit represented by the formula (MA). A plurality of As and B's may be the same or different from each other.

[0267] In one embodiment, the polymer P(IV) may further include at least one structural unit selected from the structural unit represented by the above formula (MI) and the structural unit represented by the above formula (AD). In that case, it has a structure represented by the formula (P3').

[0268]

Chemical formula

[0269] In the formula (P3'), n is an integer from 1 to 6. p, q', and r represent the molar contents of the structural units A, B', and C contained in each polymer chain within n [ ]. p, q', and r may be the same or different for each polymer chain within n [ ]. p + q' + r = 1, p is 0 or more, q' is 0 or more, and r is 0 or more. Let the molar contents of the respective structural units A, B', and C contained in the polymer be p t , q t ', and r t respectively. Then p t + q t + r t = 1. p t is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, and even more preferably 0.35 to 0.6. q t' is greater than 0, preferably from 0.10 to 0.6, more preferably from 0.2 to 0.50, still more preferably from 0.25 to 0.45, r t is greater than 0, preferably from 0.03 to 0.3, more preferably from 0.04 to 0.28, and particularly preferably from 0.05 to 0.25. Y is a monofunctional or polyfunctional thiol group-containing compound-derived organic group having 1 to 30 carbon atoms and 1 to 6 valences, A represents at least one structural unit selected from the structural unit represented by the above formula (NB), the structural unit represented by the above formula (ST), the structural unit represented by the above formula (IN), the structural unit represented by the above formula (AK), and the structural unit represented by the above formula (CA), B' represents a structural unit represented by the formula (MA), C represents at least one structural unit selected from the structural unit represented by the above formula (AD) and the structural unit represented by the above formula (MI), A plurality of As, B's, and Cs may be the same or different from each other.

[0270] Polymer P(IV) is a raw material polymer used in the production of the above-mentioned polymer P(II) and is a polymer obtained in the step of step bI.

[0271] The weight average molecular weight Mw and dispersity (weight average molecular weight Mw / number average molecular weight Mn) of polymer P(IV) are the same as the physical properties of the above-mentioned polymer P(III).

[0272] [Polymer solution] The polymer solution of the present embodiment contains the above-mentioned polymer P(I) or polymer P(II). The polymer solution of the present embodiment may contain at least one selected from polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds together with polymer P(I) or polymer P(II).

[0273] (Polyfunctional (meth)acrylic compound) The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that may be contained in the polymer solution of the present embodiment may be an unreacted product of the (meth)acrylic compound used in the above step aII or step bII in the production of the polymer P, or may be one added separately.

[0274] Examples of the polyfunctional (meth)acrylic compound that can be blended in the polymer solution include, but are not limited to, the compounds represented by the following formula (1b-p), the compounds represented by the formula (1c-p), and the compounds represented by the formula (1d-p).

[0275]

Chemical formula

[0276]

Chemical formula

[0277]

Chemical formula

[0278] The definitions and specific embodiments of k, R, X 1 , X 1 ' and X 2 in the formula (1b-p) are the same as those in the above formula (1b). Also, the definitions and specific embodiments of k, R, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 in the formula (1c-p) are the same as those in the above formula (1c).

[0279] Y in the formula (1b-p), the formula (1c-p), and the formula (1d-p) is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0280] In the compounds of formula (1b-p), formula (1c-p) and formula (1d-p) where Y is a hydrogen atom, they may be unreacted monomers (i.e., the compounds represented by formula (1b-p), formula (1c-p) and formula (1d-p)), or they can be added separately. In formula (1d-p), n is an integer of 2 or more, preferably an integer of 2 to 5, more preferably an integer of 2 to 3.

[0281] When a polyfunctional (meth)acrylic compound is blended in the polymer solution of this embodiment separately from the unreacted substances of the polyfunctional (meth)acrylic compound used in the production of polymer P(I) or polymer P(II), the blending amount can be such that the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, still more preferably 2% or less with respect to the peak area of polymer P(I) or polymer P(II).

[0282] (monofunctional (meth)acrylic compound) Examples of the monofunctional (meth)acrylic compound blended in the polymer solution of this embodiment include compounds represented by the following formula (2a-m). In formula (2a-m), X 10 and the definitions of R are the same as those in formula (2a).

[0283]

Chemical formula

[0284] When a monofunctional (meth)acrylic compound is blended in the polymer solution of this embodiment separately from the unreacted product of the monofunctional (meth)acrylic compound used in the production of polymer P(I) or polymer P(II), the blending amount can be such that the peak area derived from the monofunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and still more preferably 2% or less with respect to the peak area of polymer P(I) or polymer P(II).

[0285] The polymer solution of this embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. As the organic solvent, one or more of a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, a lactone solvent, a carbonate solvent, etc. can be used.

[0286] Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, etc. These may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but it is used in such an amount that the concentration of the non-volatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0287] [Production of Polymer Solution] The polymer solution of this embodiment can be prepared by mixing the above components by a known method. The polymer solution of this embodiment is used as a resin material of the photosensitive resin composition described below.

[0288] [Photosensitive Resin Composition] The photosensitive resin composition of this embodiment contains the above-described polymer P(I) or polymer P(II) and a photopolymerization initiator. That is, the photosensitive resin composition of this embodiment contains the above-described polymer solution of this embodiment and a photopolymerization initiator. Each component will be described below.

[0289] (Photoinitiator) Examples of the photopolymerization initiator used in the photosensitive resin composition of this embodiment include photo radical polymerization initiators. As the photo radical polymerization initiator, known compounds can be used. For example, alkylphenone compounds such as 2,2 - diethoxyacetophenone, 2,2 - dimethoxy - 2 - phenylacetophenone, 1 - hydroxycyclohexyl phenyl ketone, 2 - hydroxy - 2 - methyl - 1 - phenylpropan - 1 - one, 1 - [4 - (2 - hydroxyethoxy)phenyl] - 2 - hydroxy - 2 - methyl - 1 - propan - 1 - one, 2 - hydroxy - 1 - {4 - [4 - (2 - hydroxy - 2 - methylpropionyl)benzyl]phenyl} - 2 - methylpropan - 1 - one, 2 - methyl - 1 - (4 - methylthiophenyl) - 2 - morpholinopropan - 1 - one, 2 - benzyl - 2 - dimethylamino - 1 - (4 - morpholinophenyl) - butanone - 1, 2 - (dimethylamino) - 2 - [(4 - methylphenyl)methyl] - 1 - [4 - (4 - morpholinyl)phenyl] - 1 - butanone; benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2 - carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2 - ethylthioxanthone, 2 - isopropylthioxanthone, 2 - chlorothioxanthone, 2,4 - dimethylthioxanthone, 2,4 - diethylthioxanthone; halomethylated triazine compounds such as 2 - (4 - methoxyphenyl) - 4,6 - bis(trichloromethyl) - s - triazine, 2 - (4 - methoxynaphthyl) - 4,6 - bis(trichloromethyl) - s - triazine, 2 - (4 - ethoxynaphthyl) - 4,6 - bis(trichloromethyl) - s - triazine, 2 - (4 - ethoxycarbonylnaphthyl) - 4,6 - bis(trichloromethyl) - s - triazine; halomethylated oxadiazole compounds such as 2 - trichloromethyl - 5 - (2'-benzofuryl) - 1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - [β - (2'-benzofuryl)vinyl] - 1,3,4 - oxadiazole, 4 - oxadiazole, 2 - trichloromethyl - 5 - furyl - 1,3,4 - oxadiazole;Imidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acyloxime); Titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; Benzoic acid ester compounds such as p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid; Acridine compounds such as 9-phenylacridine; etc. are included. The photo radical polymerization initiator may be used alone or in combination of two or more kinds.; The photo radical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, based on 100 parts by mass of the polymer P100.;

[0290] By including the above components, the photosensitive resin composition of this embodiment has high sensitivity in photolithography processing and excellent alkali solubility. Therefore, the photosensitive resin composition has excellent developability and excellent processability in the photolithography method.;

[0291] (Colorant) As one aspect, the photosensitive resin composition may contain a colorant. By containing a colorant, it can be preferably used as a forming material for color filters of liquid crystal display devices and solid-state imaging devices. Various pigments or dyes can be used as the colorant.; As the pigment, an organic pigment or an inorganic pigment can be used.;

[0292] As the organic pigment, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyromethene pigments, dye lake pigments, etc. can be used.

[0293] As the inorganic pigment, white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), colored pigments (lead yellow, cadmium-based, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine, dark blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), brightening pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.

[0294] As the dye, for example, known dyes described in JP-A-2003-270428, JP-A-9-171108, JP-A-2008-50599, etc. can be used. When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one kind of colorant or two or more kinds of colorants.

[0295] The colorant (especially pigment) can be one having an appropriate average particle diameter according to the purpose and application. However, when transparency is required especially for a color filter, a small average particle diameter of 0.1 μm or less is preferable. On the other hand, when hiding power is required for paints, etc., a large average particle diameter of 0.5 μm or more is preferable.

[0296] The colorant may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc. according to the purpose and application.

[0297] When the photosensitive resin composition contains a colorant, the amount thereof may be appropriately set according to the purpose and application. However, from the perspective of achieving both coloring density and dispersion stability of the colorant, it is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0298] (Surfactant) The photosensitive resin composition of this embodiment can contain a surfactant, and a nonionic surfactant is preferred as the surfactant.

[0299] By including a nonionic surfactant, the coatability is improved when the photosensitive resin composition is applied onto a substrate to obtain a resin film, and a coating film with a uniform thickness can be obtained. In addition, residues and pattern lifting during development of the coating film can be prevented.

[0300] The nonionic surfactant is, for example, a compound containing a fluorine group (for example, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as the main skeleton. In this embodiment, it is more preferable to use a nonionic surfactant containing a fluorine-based surfactant or a silicone-based surfactant, and it is particularly preferable to use a fluorine-based surfactant. Examples of the fluorine-based surfactant include Megafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F-554, F-556, and F-557 manufactured by DIC Corporation, and Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited, etc., but are not limited thereto. When using a surfactant, the blending amount of the surfactant is preferably 0.01 to 10% by weight based on 100 parts by mass of the resin.

[0301] (Solvent) The photosensitive resin composition can typically contain a solvent. An organic solvent is preferably used as the solvent. Specifically, one or more of a ketone solvent, an ester solvent, an ether solvent, an alcohol solvent, a lactone solvent, a carbonate solvent, etc. can be used.

[0302] Examples of the solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma-butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl-n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or a mixture thereof. The amount of the solvent used is not particularly limited, but it is used in an amount such that the concentration of the non-volatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0303] (Light-shielding agent) The resin composition of this embodiment can contain a light-shielding agent. The photosensitive resin composition may contain only one kind of light-shielding agent or two or more kinds.

[0304] When the photosensitive resin composition contains a light-shielding agent, the amount thereof may be appropriately set according to the purpose and use. However, from the viewpoint of achieving both light-shielding performance and dispersion stability of the light-shielding agent, it is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0305] (Crosslinking agent) The photosensitive resin composition of this embodiment can contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it can crosslink the polymer P by the action of active chemical species generated from the photopolymerization initiator (i.e., it can chemically bond to the polymer P). The crosslinking agent may not only form a chemical bond with the polymer, but also react with other crosslinking agents to form a bond.

[0306] The crosslinking agent is preferably a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule (however, the crosslinking agent does not correspond to the aforementioned polymer). It is preferable to use a crosslinking agent having the same type of crosslinkable group (polymerizable double bond) as the crosslinkable group possessed by the polymer in terms of further improving uniform curability, sensitivity, etc. There is no particular upper limit to the number of functional groups (number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, preferably 6 or less.

[0307] Specific examples of the crosslinking agent include polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, ε-caprolactone-added dipentaerythritol hexa(meth)acrylate; Polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether; (Meth)acrylic acid 2-vinyloxyethyl, (meth)acrylic acid 3-vinyloxypropyl, (meth)acrylic acid 1-methyl-2-vinyloxyethyl, (meth)acrylic acid 2-vinyloxypropyl, (meth)acrylic acid 4-vinyloxybutyl, (meth)acrylic acid 4-vinyloxycyclohexyl, (meth)acrylic acid 5-vinyloxy pentyl, (meth)acrylic acid 6-vinyloxyhexyl, (meth)acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth)acrylic acid p-vinyloxymethylphenylmethyl, (meth)acrylic acid 2-(vinyloxyethoxy)ethyl, (meth)acrylic acid 2-(vinyloxyethoxyethoxyethoxy)ethyl and other vinyl ether group-containing (meth)acrylic acid esters; Polyfunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, ethylene oxide-added dipentaerythritol hexaallyl ether, etc.; Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; Polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl) isocyanurate, tri(methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri(acryloyloxyethyl) isocyanurate, alkylene oxide-added tri(methacryloyloxyethyl) isocyanurate, etc.; Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Polyfunctional urethane (meth)acrylates obtained by the reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc. with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.; Polyfunctional aromatic vinyls such as divinylbenzene; etc. can be mentioned.

[0308] Among them, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate, tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, and hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate are preferred.

[0309] When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only one kind of crosslinking agent or two or more kinds of crosslinking agents. When the photosensitive resin composition contains a crosslinking agent, the amount thereof may be appropriately set according to the purpose and application. As an example, the amount of the crosslinking agent can be usually 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, based on 100 parts by mass of the photosensitive resin.

[0310] (Other Additives) The photosensitive resin composition may contain components such as fillers, binder resins other than the above-mentioned polymers, acid generators, heat resistance improvers, developing aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, matting agents, defoaming agents, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, thixotropic agents, thixotropy aids, silane coupling agents, polyhydric phenol compounds, etc., according to various purposes and required characteristics.

[0311] [Uses] By forming a film using the above-mentioned photosensitive resin composition and exposing and developing the film to form a pattern, a patterned film can be obtained. This film is applied to color filters, black matrices, etc. That is, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. Also, a black matrix can be obtained by forming a pattern using a photosensitive resin composition containing a light-shielding agent. And a liquid crystal display device and a solid-state imaging device provided with a color filter and a black matrix can be manufactured. A typical procedure for forming a pattern will be described.

[0312] (Formation of Photosensitive Resin Film) For example, by applying the above photosensitive resin composition onto an arbitrary substrate and drying it as necessary, a photosensitive resin film is first obtained.

[0313] The substrate onto which the composition is applied is not particularly limited. For example, a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, a copper-clad laminate, etc. can be mentioned. The substrate may be an unprocessed substrate or a substrate on which electrodes or elements are formed on the surface. It may be surface-treated to improve adhesion.

[0314] The method for applying the photosensitive resin composition is not particularly limited. It can be carried out by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, an inkjet method, etc.

[0315] The drying of the photosensitive resin composition applied onto the substrate is typically carried out by heat treatment using a hot plate, hot air, an oven, etc. The heating temperature is usually 80 to 140°C, preferably 90 to 120°C. Also, the heating time is usually 30 to 600 seconds, preferably about 30 to 300 seconds.

[0316] The film thickness of the photosensitive resin film is not particularly limited and may be appropriately adjusted according to the pattern to be finally obtained, but it is usually 0.5 to 10 μm, preferably 1 to 5 μm. Note that the film thickness can be adjusted by the content of the solvent in the photosensitive resin composition, the coating method, etc.

[0317] (Exposure) Exposure is typically carried out by applying actinic rays to the photosensitive resin film through an appropriate photomask.

[0318] Examples of actinic rays include X-rays, electron beams, ultraviolet rays, visible light, etc. Light with a wavelength of 200 to 500 nm is preferred. In terms of pattern resolution and handleability, the light source is preferably the g-line, h-line, or i-line of a mercury lamp, and particularly preferably the i-line. Also, two or more light rays may be mixed and used. As the exposure apparatus, a contact aligner, a mirror projection, or a stepper is preferred. The exposure light amount may be appropriately adjusted according to the amount of the photosensitizer in the photosensitive resin film, etc. For example, it is about 100 to 500 mJ / cm 2 .

[0319] Note that after exposure, if necessary, the photosensitive resin film may be heated again (post-exposure bake). The temperature is, for example, 70 to 150 °C, preferably 90 to 120 °C. Also, the time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. By performing post-exposure bake, the reaction by the radicals generated from the photo radical polymerization initiator is promoted, and the curing reaction is further promoted.

[0320] (Development) By developing the exposed photosensitive resin film with an appropriate developer, a pattern can be obtained, and a substrate provided with the pattern can be manufactured. The photosensitive resin film composed of the photosensitive resin composition containing the polymer solution of the present embodiment has excellent adhesion to the substrate, so pattern peeling is suppressed in the development process.

[0321] In the development process, development can be performed using an appropriate developer by methods such as, for example, the dipping method, the paddle method, or the rotary spray method. By development, the exposed portion (in the case of a positive type) or the unexposed portion (in the case of a negative type) of the photosensitive resin film is eluted and removed, and a pattern is obtained. The usable developer is not particularly limited. For example, an aqueous alkali solution or an organic solvent can be used.

[0322] Specific examples of the aqueous alkali solution include (i) inorganic aqueous alkali solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, (ii) organic amine aqueous solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine, and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Since the polymer of this embodiment has its alkali solubility adjusted and excellent sensitivity, when a strongly basic developer such as a TMAH (tetramethylammonium hydroxide) solution is used, the pattern after exposure and development can be made into the shape as designed.

[0323] Specific examples of the organic solvent include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, ether solvents such as propylene glycol monomethyl ether, and the like. Water-soluble organic solvents such as methanol and ethanol, and surfactants, etc. may be added to the developer.

[0324] In this embodiment, it is preferable to use an aqueous alkali solution as the developer, and it is more preferable to use tetramethylammonium hydroxide, an aqueous sodium carbonate solution, or an aqueous potassium hydroxide solution. The concentration of the aqueous alkali solution is preferably 0.01 to 10% by mass, and more preferably 0.5 to 5% by mass. Through the above steps, a pattern can be obtained / a substrate with a pattern can be manufactured, but various treatments may be performed after development.

[0325] For example, after development, the pattern and the substrate may be washed with a rinse solution. Examples of the rinse solution include distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, and the like. These may be used alone or in combination of two or more.

[0326] Also, the obtained pattern may be heated to be sufficiently cured. The heating temperature is typically 150 to 400 °C, preferably 160 to 300 °C, more preferably 200 to 250 °C. The heating time is not particularly limited, but is, for example, within the range of 15 to 300 minutes. This heat treatment can be carried out using a hot plate, an oven, a temperature-programmable heating oven, or the like. As the atmosphere gas during the heat treatment, air or an inert gas such as nitrogen or argon may be used. Further, heating may be performed under reduced pressure. An example of the structure of a liquid crystal display device and / or a solid-state imaging device including a color filter and / or a black matrix is schematically shown in FIG. 1. Note that the black matrix may be a black bank, but hereinafter, a liquid crystal display device and / or a solid-state imaging device including a color filter and a black matrix will be described.

[0327] A black matrix 11 and a color filter 12 are formed on a substrate 10. Further, a protective film 13 and a transparent electrode layer 14 are provided on the upper portions of the black matrix 11 and the color filter 12.

[0328] The substrate 10 is usually composed of a material that allows light to pass through. For example, in addition to glass, it is composed of polyester, polycarbonate, polyolefin, polysulfone, a polymer of cyclic olefin, or the like. The substrate 10 may be subjected to corona discharge treatment, ozone treatment, chemical solution treatment, or the like as necessary. The substrate 10 is preferably composed of glass. The black matrix 11 is composed of, for example, a cured product of a photosensitive resin composition containing a light-shielding agent.

[0329] As the color filter 12, usually, three colors of red, green, and blue exist. The color filter 12 is composed of a cured product of a photosensitive resin composition containing a colorant corresponding to each color.

[0330] The embodiments of the present invention have been described above. These are examples of the present invention, and various configurations other than the above can also be adopted.

Example

[0331] Hereinafter, the present invention will be described by way of examples and comparative examples, but the present invention is not limited thereto.

[0332] The compounds used in the examples may be indicated by the following abbreviations or trade names. ·MAN: Maleic anhydride ·NB: 2-Norbornene ·ST: Styrene ·IN: Indene ·DCE: 1-Decene ·HXE: 1-Hexene ·UDE: 10-Undecenoic acid ·PTE: 4-Pentenoic acid ·FADE: Diethyl fumarate ·FABEH: Bis(2-ethylhexyl) fumarate ·HMI: Maleimide ·PhMI: N-Phenylmaleimide ·MEK: Methyl ethyl ketone ·GMA: Glycidyl methacrylate ·PEMP: Pentaerythritol tetrakis(3-mercaptopropionate), thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemical Co., Ltd.) ·4-HBA: 4-Hydroxybutyl acrylate ·A-TMM-3LM-N: A mixture of the following two compounds. The amount of the left compound in the mixture based on gas chromatographic measurement is about 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0333]

Chemical formula

[0334] <Synthesis of raw material polymer> (Synthesis of raw material polymer 1) Into a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 602.56 g of a 75% toluene solution of 2-norbornene (451.92 g in terms of 2-norbornene, 4.8 mol), 470.69 g of maleic anhydride (MAN) (4.8 mol), and 2281.74 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Next, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated. When the internal temperature reached 80 °C, a solution prepared by dissolving 44.21 g (0.19 mol) of 2,2'-azobisisobutyronitrile (manufactured by Fuji Film Wako Pure Chemical Industries, trade name: V-601) and 93.82 g (0.19 mol) of PEMP in 193.4 g of MEK was added over 1 hour. Then, the reaction was further carried out at 80 °C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 3686.4 g of methanol to precipitate a white solid. The obtained white solid was further washed with 3686.4 g of methanol and then vacuum dried at a temperature of 120 °C to obtain 910.1 g of a polymer (raw material polymer 1) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. As a result of measuring the obtained raw material polymer 1 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,500, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.62.

[0335] (Confirmation of the thioether structure contained in the raw material polymer 1) Regarding the PEMP monomer represented by the following chemical formula 13 By 13C-NMR measurement, peak a derived from carbon a was confirmed at around 19.0 ppm, and peak b derived from carbon b was confirmed at around 62.0 ppm.

[0336]

Chemical formula

[0337] Regarding the raw material polymer 1 synthesized using PEMP 13In the 13C-NMR measurement, the appearance of peak b derived from carbon b was confirmed at around 62.0 ppm. In the GPC measurement of the reaction solution, no peak of the PEMP monomer was observed, indicating that no unreacted PEMP remained. Thus, it was confirmed that PEMP was incorporated into the raw material polymer 1.

[0338] Also, in the 13 13C-NMR measurement of the raw material polymer 1, peak a derived from carbon a was not confirmed. Instead, a peak c corresponding to thioether (R-S-R') appeared at around 28 ppm. Since the integral value of this peak c was approximately twice that of peak b, the raw material polymer 1 had a skeleton with a thioether group as follows, and the thiol group had disappeared.

[0339]

Chemical formula

[0340] 13 The conditions for the 13C-NMR measurement are as follows. (Test conditions) The measurement sample was prepared by adding a measurement solvent to the weighed sample to adjust the concentration, and then injecting a specified amount into an NMR measurement sample tube. · Measuring device: JEOL JNM-ECA400 superconducting FT-NMR device · Resonance frequency: 100.53 MHz · Measured nucleus: 13 13C · Measurement method: NNE measurement (inverse gated decoupling method) · Pulse width: 3.83 μsec · Pulse repetition waiting time: 30 s · Number of integrations: 4096 times · Measurement temperature: Room temperature · Measurement solvent: DMSO-d6 (deuterated dimethyl sulfoxide) · Sample concentration: 20% (w / v) The sulfur content in the obtained polymer was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that sulfur elements were present in the polymer. Also, in the GPC measurement of the reaction solution before the addition of methanol, the peak derived from PEMP had disappeared, confirming that PEMP was incorporated into the raw material polymer 1.

[0341] As a result of elemental analysis, the sulfur content in the raw material polymer 1 was 2.4 wt%.

[0342] (Synthesis of raw material polymer 2) Into a reaction vessel equipped with a stirrer, a condenser, and a dropping funnel, 122.40 g (1.18 mol) of styrene (ST), 115.24 g (1.18 mol) of maleic anhydride (MAN), and 1940.42 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated, and when the internal temperature reached 80 °C, a solution prepared by dissolving 2,2'-azobisisobutyronitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.82 g, 0.047 mol) and pentaerythritol tetrakis(3-mercaptopropionate) (PEMP, 22.97 g, 0.047 mol) in 164.49 g of MEK was added over 1 hour. Thereafter, the reaction was further carried out at 80 °C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 3686.4 g of methanol to precipitate a white solid. The obtained white solid was further washed with 3686.4 g of methanol and then vacuum dried at a temperature of 120 °C to obtain 237.1 g of a polymer (raw material polymer 2) having a structural unit derived from styrene and a structural unit derived from maleic anhydride. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 14,600, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 5.11.

[0343] The sulfur content in the obtained raw material polymer 2 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 2. Also, in the GPC measurement of the reaction solution before dropping methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0344] (Synthesis of raw material polymer 3) 122.4 g (1.05 mol) of indene (IN), 131.0 g of methyl ethyl ketone (MEK), and 3.73 g (0.016 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed and placed in a reaction vessel of appropriate size equipped with a stirrer and a cooling tube, and stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, the temperature was raised, and when the internal temperature reached 55°C, 103.2 g (1.05 mol) of maleic anhydride (MAN) and pentaerythritol tetrakis(3-mercaptopropionate) (PEMP, 20.58 g, 0.042 mol) dissolved in 131.02 g of MEK were added dropwise over 3 hours after removing the dissolved oxygen in the system by nitrogen bubbling. Then, by further heating at 55°C for 3 hours, maleic anhydride and indene were polymerized to prepare a polymerization solution. The polymerization solution obtained above was dropped into 2047.94 g of methanol to precipitate a white solid. The obtained white solid was further washed with 2047.94 g of methanol and then vacuum dried at a temperature of 120°C to obtain 315.0 g of a polymer (raw material polymer 3) having a structural unit derived from indene and a structural unit derived from maleic anhydride. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 8,300, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.41.

[0345] (Raw material polymer 4) XIRAN (registered trademark) 1000, a copolymer composed of a structural unit derived from styrene and a structural unit derived from maleic anhydride (manufactured by Maruzen Petrochemical Co., Ltd., styrene maleic anhydride copolymer, (styrene: maleic acid ratio = 1:1)), was prepared and used as the raw material polymer 4. The weight average molecular weight Mw of the raw material polymer 4 was 6,500, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 2.51.

[0346] (Synthesis of raw material polymer 5) Into a reaction vessel equipped with a stirrer, a cooling pipe, and a dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (84.75 g in terms of 2-norbornene, 0.900 mol), 88.25 g of maleic anhydride (MAN) (0.900 mol), 102.73 g of dibutyl fumarate (FADB) (0.450 mol), and 179.12 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated, and when the internal temperature reached 70°C, a solution prepared by dissolving 10.36 g (0.045 mol) of 2,2'-azobisisobutyronitrile dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-601) and 32.98 g (0.0675 mol) of PEMP in 76.77 g of MEK was added over 1 hour. Further, the temperature was raised to 80°C, and the reaction was carried out at 80°C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 3016.2 g of methanol to precipitate a white solid. The obtained white solid was further washed with 754.1 g of methanol and then vacuum dried at a temperature of 120°C to obtain 154.2 g of a polymer (raw material polymer 5) having a structural unit derived from 2-norbornene, a structural unit derived from dibutyl fumarate, and a structural unit derived from maleic anhydride. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,800, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.54.

[0347] [Structural analysis of raw material polymer 5] The synthesis of the raw material polymer 5 starts with the monomers and PEMP dissolved in the solvent at the beginning of the reaction, and then the reaction proceeds to form the polymer. Analysis of each of the reaction solution and the obtained polymer gave the following results.

[0348] (a) Analysis of the reaction solution In the GPC measurement of the reaction solution before reprecipitation purification, no peak of PEMP alone was observed. That is, it was confirmed that no PEMP remained in the reaction solution. Also, in the GC (gas chromatography) measurement of the reaction solution before reprecipitation purification, compared with before the reaction, the peaks of norbornene monomer, dibutyl fumarate monomer, and maleic anhydride monomer in the reaction solution after the reaction decreased, and it was confirmed that norbornene monomer, dibutyl fumarate, and maleic anhydride reacted to form the polymer.

[0349] (b) Analysis of the polymer In the GPC measurement of the polymer after reprecipitation purification, no peaks of PEMP monomer, norbornene monomer, dibutyl fumarate monomer, and maleic anhydride monomer were observed. That is, it was confirmed that no PEMP, norbornene monomer, dibutyl fumarate monomer, and maleic anhydride monomer remained in the polymer.

[0350] Regarding the raw material polymer 5, 13 The ratio of the structures derived from each monomer actually introduced into the raw material polymer calculated by C-NMR was norbornene:dibutyl fumarate:maleic anhydride = 48.0%:9.0%:46.7%, and the amount of PEMP actually introduced into the raw material polymer was 3.4 mol% based on the total amount of each monomer.

[0351] The sulfur content in the obtained raw material polymer 5 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 4. Also, in the GPC measurement of the reaction solution before dropping methanol, the peak derived from PEMP disappeared, and it was confirmed that PEMP was incorporated into the polymer.

[0352] (Confirmation of the Structure of Raw Material Polymer 5) In the raw material polymer 5, the amounts (mole fraction, mol%) of the structural unit derived from PEMP, the structural unit derived from dibutyl fumarate (FADB) (structural unit of formula (AD)), the structural unit derived from maleic anhydride (MAN) (structural unit of formula (MA)), and the structure derived from norbornene (NB) (structural unit of formula (NB)) were 13 calculated by integral value analysis of C-NMR. 13 The C-NMR chart is shown in Figure 2. 13 The chemical shifts of the C-NMR chart were assigned to each structural unit as follows, and the corresponding integral values were measured. · k(4C) of PEPM: 62.0 - 64.0 ppm · Alkyl terminal (2C) of FADB: 13.0 - 15.0 ppm · Maleic anhydride ester (2C) + g(4C) of PEMP: 170.0 - 174.7 ppm · Maleic acid ester (2C) + ester (2C) of FADB: 174.7 - 178.0 ppm · Alkyl chain: 20 - 60 ppm · DMSO: around 40 ppm · Norbornene (7C) = Alkyl chain - DMSO - PEMP (9C, h + i + j) - Maleic anhydride (2C) - Maleic acid (2C) - FADB (6C) Here, the structural ratio of maleic anhydride actually introduced into the raw material polymer was calculated including the structure of maleic acid formed by ring-opening of maleic anhydride in addition to the structural unit of formula (MA).

[0353] (Synthesis of Raw Material Polymer 6) Except that 153.22 g (0.450 mol) of bis(2-ethylhexyl) fumarate (FABEH) was used instead of dibutyl fumarate (FADB), in the same manner as raw material polymer 5, 169.1 g of a polymer (raw material polymer 6) having a structural unit derived from 2-norbornene, a structural unit derived from bis(2-ethylhexyl) fumarate, and a structural unit derived from maleic anhydride was obtained. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,900, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.59.

[0354] The sulfur content in the obtained raw material polymer 6 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 6. Also, in the GPC measurement of the reaction solution before dropping methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0355] (Synthesis of raw material polymer 7) Into a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 88.25 g (0.900 mol) of maleic anhydride (MAN), 102.73 g (0.450 mol) of dibutyl fumarate (FADB), and 701.16 g of 4-methyl-2-pentanone (MIBK) were added and stirred and dissolved. Next, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated, and when the internal temperature reached 90 °C, a solution prepared by dissolving 117.14 g (1.125 mol) of styrene (ST), 11.74 g (0.051 mol) of 2,2'-azobisisobutyronitrile dimethyl (manufactured by Fuji Film Wako Pure Chemical Industries, trade name: V-601), and PEMP (36.28 g, 0.074 mol) in 175.29 g of 4-methyl-2-pentanone (MIBK) was added over 2 hours. The reaction was further carried out at 80 °C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 6848.0 g of methanol to precipitate a white solid. The obtained white solid was further washed with 3424.0 g of methanol and then vacuum dried at a temperature of 120 °C to obtain 307.0 g of a polymer (raw material polymer 7) having a structural unit derived from styrene, a structural unit derived from dibutyl fumarate, and a structural unit derived from maleic anhydride. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 4,364, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 2.15.

[0356] The sulfur content in the obtained raw material polymer 7 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 7. Also, in the GPC measurement of the reaction solution before dropping methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0357] (Synthesis of raw material polymer 8) Into a reaction vessel equipped with a stirrer, a condenser, and a dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (84.75 g in terms of 2-norbornene, 0.900 mol), 88.26 g of maleic anhydride (MAN) (0.900 mol), 31.56 g of 1-decene (DCE) (0.225 mol), 102.73 g of dibutyl fumarate (FADB) (0.450 mol), and 245.36 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Next, after removing dissolved oxygen in the system by nitrogen bubbling, the mixture was heated, and when the internal temperature reached 70°C, a solution prepared by dissolving 10.36 g (0.045 mol) of 2,2'-azobis(isobutyric acid) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-601) and PEMP (36.28 g, 0.074 mol) in 48.20 g of MEK was added over 1 hour. Further, the temperature was raised to 80°C, and the reaction was carried out at 80°C for 7 hours after the temperature rise. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 4033.0 g of methanol to precipitate a white solid. The obtained white solid was further washed with 2689.0 g of methanol and then vacuum dried at a temperature of 120°C to obtain 227.4 g of a polymer (raw material polymer 8) having a structural unit derived from 2-norbornene, a structural unit derived from 1-decene, a structural unit derived from dibutyl fumarate, and a structural unit derived from maleic anhydride. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,900, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.67.

[0358] (Synthesis of Raw Material Polymer 9) Into a reaction vessel equipped with a stirrer, a cooling pipe, and a dropping funnel, 141.22 g (1.68 mol) of 1 - hexene (HXE), 164.54 g (1.68 mol) of maleic anhydride (MAN), 337.39 g of methyl ethyl ketone (MEK), and 15.45 g (0.067 mol) of 2,2'-azobis(isobutyronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V - 601) were added and stirred and dissolved. Next, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated and reacted at 65 °C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 5317.12 g of methanol to precipitate a white solid. The obtained white solid was further washed with 5317.12 g of methanol and then vacuum dried at a temperature of 120 °C to obtain 140.5 g of a polymer (raw material polymer 9) having a structural unit derived from 1 - hexene and a structural unit derived from maleic anhydride. As a result of measuring the obtained raw material polymer 9 using gel permeation chromatography (GPC), the weight - average molecular weight Mw was 10,500, and the polydispersity (weight - average molecular weight Mw) / (number - average molecular weight Mn) was 2.35. Regarding raw material polymer 9, 13 The ratio of the structures derived from each monomer actually introduced into the raw material polymer calculated by C - NMR was 1 - hexene:maleic anhydride = 44.2%:55.8%.

[0359] [Confirmation of the Structure of Raw Material Polymer 9] In raw material polymer 9, the structural unit derived from 1 - hexene (structural unit of formula (AK)) and the structural unit derived from maleic anhydride (structural unit of formula (MA)) were 13 calculated by C - NMR integral value analysis. 13 The C - NMR chart is shown in Figure 3. 13 The chemical shifts of the C - NMR chart were assigned to each structural unit as follows, and the corresponding integral values were measured. · 1 - hexene terminal (1C): 13.0 - 15.0 ppm · Maleic anhydride ester (2C): 170.0~174.7 ppm Here, the structural ratio of maleic anhydride actually introduced into the raw material polymer was calculated including the structural unit of formula (MA) and also the structure of maleic acid formed by ring-opening of maleic anhydride.

[0360] (Synthesis of raw material polymer 10) Into a reaction vessel equipped with a stirrer, a cooling pipe, and a dropping funnel, 403.97 g (4.8 mol) of 1-hexene (HXE), 470.69 g (4.8 mol) of maleic anhydride (MAN), and 871.09 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Next, after removing dissolved oxygen in the system by nitrogen bubbling, the mixture was heated, and when the internal temperature reached 65 °C, a solution prepared by dissolving 90.19 g (0.392 mol) of 2,2'-azobisisobutyronitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-601) and PEMP (93.82 g, 0.19 mol) in 463.10 g of MEK was added over 1 hour. Then, the reaction was further carried out at 65 °C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 3686.4 g of methanol to precipitate a white solid. The obtained white solid was further washed with 3686.4 g of methanol and then vacuum dried at a temperature of 120 °C to obtain 350.2 g of a polymer (raw material polymer 10) having a structural unit derived from 1-hexene and a structural unit derived from maleic anhydride. As a result of measuring the obtained raw material polymer 10 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,800, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.43. The sulfur content in the obtained raw material polymer 10 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 10. Also, in the GPC measurement of the reaction solution before dropping methanol, the peak derived from PEMP had disappeared, confirming that PEMP was incorporated into the polymer.

[0361] Regarding the raw material polymer 10, 13The ratio of the structures derived from each monomer actually introduced into the raw material polymer calculated by 13C-NMR was 1-hexene: maleic anhydride = 45.7%: 54.3%, and the amount of PEMP actually introduced into the raw material polymer was 2.9 mol% based on the total amount of each monomer.

[0362] [Confirmation of the Structure of Raw Material Polymer 10] In raw material polymer 10, the structural units derived from PEMP, the structural units derived from 1-hexene (structural units of formula (AK)), and the structural units derived from maleic anhydride (structural units of formula (MA)) 13 were calculated by 13C-NMR integral value analysis. 13 The chemical shifts of the 13C-NMR chart were assigned to each structural unit as follows, and the corresponding integral values were measured. · k(4C) of PEMP: 62.0 to 64.0 ppm · 1-hexene terminal (1C): 13.0 to 15.0 ppm · Maleic anhydride ester (2C) + g(4C) of PEMP: 170.0 to 174.7 ppm · Maleic acid ester (2C) (structure in which maleic anhydride is ring-opened): 174.7 to 178.0 ppm Here, the structural ratio of maleic anhydride actually introduced into the raw material polymer was calculated including the structural unit of formula (MA) and the structure of maleic acid in which maleic anhydride was ring-opened.

[0363] (Synthesis of Raw Material Polymer 11) Into a reaction vessel equipped with a stirrer, a cooling pipe, and a dropping funnel, 88.25 g (0.900 mol) of maleic anhydride (MAN), 126.23 g (1.500 mol) of 1-hexene (HXE), 58.24 g (0.600 mol) of maleimide (HMI), and 271.52 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Then, after removing dissolved oxygen in the system by nitrogen bubbling, the mixture was heated. When the internal temperature reached 65 °C, a solution prepared by dissolving 2,2'-azobisisobutyronitrile (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., trade name: V-601, 28.18 g, 0.122 mol) and PEMP (29.32 g, 0.060 mol) in 144.35 g of MEK was added over 1 hour. The reaction was further carried out at 65 °C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 5969.0 g of isopropanol to precipitate a white solid. The obtained white solid was further washed with 746.0 g of isopropanol and then vacuum dried at a temperature of 120 °C to obtain 146.6 g of a polymer (raw material polymer 11) having a structural unit derived from 1-hexene, a structural unit derived from maleimide, and a structural unit derived from maleic anhydride. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 4,100, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.66.

[0364] The sulfur content in the obtained raw material polymer 11 was confirmed by elemental analysis by flask combustion and ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 11. Also, in the GPC measurement of the reaction solution before dropping methanol, the peak derived from PEMP disappeared, and it was confirmed that PEMP was incorporated into the polymer. Regarding the raw material polymer 11, 13 The ratio of the structures derived from each monomer actually introduced into the raw material polymer calculated by C-NMR was 1-hexene: maleic anhydride: maleimide = 39.8%: 38.0%: 22.2%, and the amount of PEMP actually introduced into the raw material polymer was 2.4 mol% based on the total amount of each monomer.

[0365] [Determination of the Structure of Raw Material Polymer 11] In the raw material polymer 11, the amounts (mole fraction, mol%) of the structural unit derived from PEMP, the structural unit derived from 1-hexene (structural unit of formula (AK)), the structural unit derived from maleic anhydride (structural unit of formula (MA)), and the structure derived from maleimide (structural unit of formula (MI)) were 13 calculated by integral value analysis of C-NMR. 13 The chemical shifts of the C-NMR chart were assigned to each structural unit as follows, and the corresponding integral values were measured. · k(4C) of PEMP: 62.0 to 64.0 ppm · 1-hexene terminal (1C): 13.0 to 15.0 ppm · Maleic anhydride ester (2C) + g(4C) of PEMP: 170.0 to 174.7 ppm · Maleic acid ester (2C) (structure in which maleic anhydride has ring-opened): 174.7 to 178.0 ppm · MI ester (2C): 178.0 to 183.0 ppm Here, the structural ratio of maleic anhydride actually introduced into the raw material polymer was calculated including the structural unit of formula (MA) and also the structure of maleic acid in which maleic anhydride has ring-opened.

[0366] (Synthesis of Raw Material Polymer 12) Into a reaction vessel equipped with a stirrer, a cooling pipe, and a dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (84.75 g in terms of 2-norbornene, 0.900 mol), 110.32 g of maleic anhydride (MAN) (1.125 mol), 31.56 g of 1-decene (DCE) (0.225 mol), and 569.75 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Next, after removing dissolved oxygen in the system by nitrogen bubbling, the mixture was heated. When the internal temperature reached 80 °C, a solution prepared by dissolving 2,2'-azobis(isobutyric acid) dimethyl (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.36 g, 0.045 mol) and PEMP (21.99 g, 0.045 mol) in 48.20 g of MEK was added over 1 hour. The reaction was further carried out at 80 °C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 3621.5 g of methanol to precipitate a white solid. The obtained white solid was further washed with 905.4 g of methanol and then vacuum-dried at a temperature of 120 °C to obtain 180.1 g of a polymer (raw material polymer 12) having a structural unit derived from 2-norbornene, a structural unit derived from 1-decene, and a structural unit derived from maleic anhydride. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,700, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.77. Regarding raw material polymer 12, 13 The ratio of the structures derived from each monomer actually introduced into the raw material polymer calculated by C-NMR was norbornene: maleic anhydride: 1-decene = 42.0%: 51.0%: 7.0%, and the amount of PEMP actually introduced into the raw material polymer was 2.9 mol% based on the total amount of each monomer.

[0367] [Confirmation of the structure of raw material polymer 12] In raw material polymer 12, the amounts (mole fraction, mol%) of the structural unit derived from PEMP, the structural unit derived from 1-decene (structural unit of formula (AK)), the structural unit derived from maleic anhydride (structural unit of formula (MA)), and the structure derived from norbornene (structural unit of formula (NB))13 It was calculated by the integral value analysis of 13C-NMR. 13 The 13C-NMR chart is shown in Figure 4. 13 The chemical shifts of the 13C-NMR chart were assigned to each structural unit as follows, and the corresponding integral values were measured. · k(4C) of PEMP: 62.0 to 64.0 ppm · 1-decene terminal (1C): 13.0 to 15.0 ppm · Maleic anhydride ester (2C) + g(4C) of PEMP: 170.0 to 174.7 ppm · Maleic acid ester (2C) (structure in which maleic anhydride is ring-opened): 174.7 to 178.0 ppm · Alkyl chain: 20 to 60 ppm · DMSO: around 40 ppm · Norbornene (7C) = alkyl chain - DMSO - PEMP (9C, h + i + j) - maleic anhydride (2C) - maleic acid (2C) - decene (9C) Here, the structural ratio of maleic anhydride-derived structures actually introduced into the raw material polymer was calculated including the structure of maleic acid in which maleic anhydride was ring-opened in addition to the structural unit of formula (MA).

[0368] The sulfur content in the obtained raw material polymer 12 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 12. Also, in the GPC measurement of the reaction solution before dropping methanol, the peak derived from PEMP disappeared, and it was confirmed that PEMP was incorporated into the polymer.

[0369] (Synthesis of raw material polymer 13) Into a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (84.75 g in terms of 2-norbornene, 0.900 mol), 110.32 g of maleic anhydride (MAN) (1.125 mol), 22.53 g of 4-pentenoic acid (0.225 mol), and 597.10 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated. When the internal temperature reached 80°C, a solution prepared by dissolving 2,2'-azobisisobutyronitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.36 g, 0.045 mol) and PEMP (21.99 g, 0.045 mol) in 50.51 g of MEK was added over 1 hour. The reaction was further carried out at 80°C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 3621.5 g of methanol to precipitate a white solid. The obtained white solid was further washed with 905.4 g of methanol and then vacuum dried at a temperature of 120°C to obtain 162.5 g of a polymer (raw material polymer 13) comprising a structural unit derived from 2-norbornene, a structural unit derived from 4-pentenoic acid, and a structural unit derived from maleic anhydride. The resulting polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 2,700, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.96.

[0370] The sulfur content in the obtained raw material polymer 13 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 13. Also, in the GPC measurement of the reaction solution before the addition of methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0371] (Synthesis of raw material polymer 14) Into a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (84.75 g in terms of 2-norbornene, 0.900 mol), 110.32 g of maleic anhydride (MAN) (1.125 mol), 31.56 g of 1-decene (DCE) (0.225 mol), and 569.75 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Then, after removing dissolved oxygen in the system by nitrogen bubbling, the mixture was heated. When the internal temperature reached 80 °C, a solution prepared by dissolving 10.36 g (0.045 mol) of 2,2'-azobis(isobutyronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-601) in 48.20 g of MEK was added over 1 hour. The reaction was further carried out at 80 °C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 3621.5 g of methanol to precipitate a white solid. The obtained white solid was further washed with 905.4 g of methanol and then vacuum dried at 120 °C to obtain 153.0 g of a polymer (raw material polymer 14) having a structural unit derived from 2-norbornene, a structural unit derived from 1-decene, and a structural unit derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 4,700, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 2.26.

[0372] (Synthesis of raw material polymer 15) Into a reaction vessel equipped with a stirrer, a cooling pipe, and a dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (84.75 g in terms of 2-norbornene, 0.900 mol), 110.32 g of maleic anhydride (MAN) (1.125 mol), 41.46 g of 10-undecenoic acid (UDE) (0.225 mol), and 597.10 g of methyl ethyl ketone (MEK) were added and stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, the mixture was heated, and when the internal temperature reached 80 °C, a solution prepared by dissolving 2,2'-azobisisobutyronitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.36 g, 0.045 mol) and PEMP (21.99 g, 0.045 mol) in 50.51 g of MEK was added over 1 hour. Further, the reaction was carried out at 80 °C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 3621.5 g of methanol to precipitate a white solid. The obtained white solid was further washed with 905.4 g of methanol and then vacuum dried at a temperature of 120 °C to obtain 172.1 g of a polymer (raw material polymer 15) comprising a structural unit derived from 2-norbornene, a structural unit derived from 10-undecenoic acid, and a structural unit derived from maleic anhydride. The resulting polymer was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight Mw was 3,200, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.66.

[0373] The sulfur content in the obtained raw material polymer 15 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 15. Also, in the GPC measurement of the reaction solution before dropping methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0374] (Synthesis of raw material polymer 16) Except that 22.53 g (0.225 mol) of 4-pentenoic acid was used instead of 10-undecenoic acid, in the same manner as the raw material polymer 4, 162.5 g of a polymer (raw material polymer 16) having a structural unit derived from 2-norbornene, a structural unit derived from 4-pentenoic acid, and a structural unit derived from maleic anhydride was obtained. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,700, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.96. The sulfur content in the obtained raw material polymer 16 was confirmed by elemental analysis by flask combustion and ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 16. Also, in the GPC measurement of the reaction solution before dropping methanol, the peak derived from PEMP disappeared, and it was confirmed that PEMP was incorporated into the polymer.

[0375] (Synthesis of raw material polymer 17) Into a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 88.25 g (0.900 mol) of maleic anhydride (MAN) and 526.09 g of 4-methyl-2-pentanone (MIBK) were added and stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, the temperature was raised, and when the internal temperature reached 90 °C, a solution prepared by dissolving 93.74 g (0.900 mol) of styrene (ST), 17.57 g (0.076 mol) of 2,2'-azobisisobutyronitrile dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-601), and PEMP (52.77 g, 0.108 mol) in 131.52 g of 4-methyl-2-pentanone (MIBK) was added over 2 hours. Further, the reaction was carried out at 80 °C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 4044.0 g of methanol to precipitate a white solid. The obtained white solid was further washed with 2022.0 g of methanol and then vacuum dried at a temperature of 120 °C to obtain 145.1 g of a polymer (raw material polymer 17) having a structural unit derived from styrene and a structural unit derived from maleic anhydride. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,400, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.83.

[0376] The sulfur content in the obtained raw material polymer 17 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 17. Also, in the GPC measurement of the reaction solution before dropping methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0377] (Synthesis of raw material polymer 18) 88.25 g (0.900 mol) of maleic anhydride (MAN) and 526.09 g of methyl ethyl ketone (MEK) were added to a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, and stirred and dissolved. Next, after removing dissolved oxygen in the system by nitrogen bubbling, the temperature was raised, and when the internal temperature reached 90 °C, a solution prepared by dissolving 93.74 g (0.900 mol) of styrene (ST), 17.57 g (0.076 mol) of 2,2'-azobisisobutyronitrile dimethyl (manufactured by Fuji Film Wako Pure Chemical Industries, trade name: V-601), and PEMP (70.36 g, 0.144 mol) in 131.52 g of methyl ethyl ketone (MEK) was added over 2 hours. Further, the reaction was carried out at 80 °C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 4044.0 g of methanol to precipitate a white solid. The obtained white solid was further washed with 2022.0 g of methanol and then vacuum dried at a temperature of 120 °C to obtain 212.5 g of a polymer (raw material polymer 18) having a structural unit derived from styrene and a structural unit derived from maleic anhydride. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,300, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.72.

[0378] The sulfur content in the obtained raw material polymer 18 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 18. Also, in the GPC measurement of the reaction solution before the addition of methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0379] (Synthesis of Raw Material Polymer 19) Into a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 79.43 g (0.810 mol) of maleic anhydride (MAN), 15.99 g (0.090 mol) of N-phenylmaleimide, and 547.72 g of 4-methyl-2-pentanone (MIBK) were added and stirred and dissolved. Then, after removing the dissolved oxygen in the system by nitrogen bubbling, the temperature was raised. When the internal temperature reached 90 °C, a solution prepared by dissolving 93.74 g (0.900 mol) of styrene (ST), 17.57 g (0.076 mol) of 2,2'-azobisisobutyronitrile dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-601), and PEMP (52.77 g, 0.108 mol) in 136.93 g of 4-methyl-2-pentanone (MIBK) was added over 2 hours. The reaction was further carried out at 80 °C for 7 hours. Then, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was dropped into 4194.0 g of methanol to precipitate a white solid. The obtained white solid was further washed with 2097.0 g of methanol and then vacuum-dried at a temperature of 120 °C to obtain 166.7 g of a polymer (raw material polymer 19) having a structural unit derived from styrene, a structural unit derived from N-phenylmaleimide, and a structural unit derived from maleic anhydride. As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,800, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.70.

[0380] The sulfur content in the obtained raw material polymer 19 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that sulfur elements were present in the raw material polymer 19. Also, in the GPC measurement of the reaction solution before dropping methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0381] For raw material polymers 3 to 11, the amount of each monomer in the reaction solution before and after the reaction was measured by gas chromatography (GC) measurement, and the consumption amount of each monomer was calculated to calculate the ratio of each monomer introduced into the raw material polymer. Table 1 below shows the charging ratio of the monomers used in the synthesis of the raw material polymer, the ratio of the monomers introduced into the raw material polymer, the weight average molecular weight (Mw) of the raw material polymer, and the polydispersity (Mw / Mn). The measurement conditions for gas chromatography measurement are as follows. · GC device: GC-2030 (Shimadzu Corporation) · Carrier gas: N2 · Detector: Flame ionization detector (FID), FID temperature: 300 °C · Column: SH-RXi-1HT, inner diameter 0.25, length 30 m, film thickness 0.25 μm (Shimadzu GLC Corporation) · Vaporization chamber temperature: 210 °C · Column flow rate: 0.64 mL / min · Column temperature rising condition: Hold at 50 °C for 5 min, rise to 300 °C at 20 °C / min, hold at 300 °C for 10 min

[0382]

Table 1

[0383] <Synthesis of Polymer P> Polymer P was prepared using the following method.

[0384] (Preparation Example 1) The MA units of the raw material polymer 1 were ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to produce polymer P1. The details are described below. First, 99.93 g of MEK was added to 60.00 g of the raw material polymer 1 (0.312 mol in terms of MA calculated from the charged amount of the raw material polymer 1) to prepare a solution. Next, 77.49 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at 70 °C for 2 hours. Subsequently, 56.27 g (0.390 mol) of 4-HBA was added, and the reaction was carried out at 70 °C for 4 hours to prepare a reaction solution. Next, without post-treating the obtained reaction solution, 3.00 g (0.167 mol) of water was added to this reaction solution, and the reaction was carried out at 70 °C for 2 hours. The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Further, liquid-liquid extraction and then solvent replacement were carried out according to the following procedures. · Liquid-liquid extraction: The reaction solution was diluted with MEK, then water was added and treated to remove the aqueous phase from the reaction solution, and then the same operation was carried out once more. · Solvent replacement: The obtained reaction mixture was subjected to solvent removal at 50 °C under reduced pressure using a rotary evaporator. It was confirmed that the solid content concentration of the polymer solution became 27 ± 2% by mass as measured by a heat drying type moisture meter, and the operation of solvent removal was interrupted. Then, PGMEA was added so that the solid content concentration became 18% by mass, and the mixture was stirred until it became uniform. The operation of solvent removal at 50 °C under reduced pressure was carried out in the same manner, and after adjusting the solid content concentration to 27 ± 2% by mass as measured by a heat drying type moisture meter, the operation of adding PGMEA so that the solid content concentration became 18% by mass and stirring until it became uniform was repeated 2 more times. Then, the operation of solvent removal or adding PGMEA so that the solid content concentration became 30 ± 3% by mass and stirring until it became uniform was carried out. By the above operations, the solvent used in the reaction was removed, and the solvent was replaced with PGMEA. Then, it was further purified according to the following procedure. · The polymer was reprecipitated with an excess amount of toluene. · The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of toluene was repeated twice. · The operation of washing the polymer powder after the above two washings with an excessive amount of water was carried out three times. · The obtained reaction product was dried at 40 °C for 12 hours. Thus, a polymer P1 in which the MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared. For the obtained polymer P1, GPC measurement was carried out to measure the weight-average molecular weight and polydispersity of the polymer P1. The results are shown in Table 2. Also, by GPC measurement of the polymer P1, the disappearance of the peaks of the trifunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed. Thereby, it was confirmed that the obtained polymer P1 does not contain unreacted trifunctional (meth)acrylic compound or monofunctional (meth)acrylic compound. Also 13 By C-NMR measurement, it was confirmed that the polymer P1 has a structure in which the structural unit derived from maleic anhydride is ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0385] (Preparation Example 2) A polymer P2 in which the MA unit of the raw material polymer 2 was ring-opened with a monofunctional (meth)acrylic compound was prepared. The details are described below. First, 18.44 g of MEK was added to 10.00 g (0.049 mol in terms of MA) of the raw material polymer 2 to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70 °C for 6 hours to prepare a reaction solution. The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Thereafter, the polymer was purified by the following reprecipitation method. · Reprecipitation method: The polymer was reprecipitated with an excessive amount of water. The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of water was repeated twice. The obtained reaction product was dried at 40 °C for 12 hours. As described above, 8.0 g of polymer P2 was obtained, in which the structural unit derived from maleic anhydride in raw material polymer 2 was ring-opened with 4-HBA. For the obtained polymer P2, GPC measurement was carried out to measure the weight-average molecular weight and polydispersity of polymer P2. The results are shown in Table 2. Also, by GPC measurement of polymer P2, disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P2 does not contain unreacted monofunctional (meth)acrylic compound.

[0386] (Preparation Example 3) Except that raw material polymer 2 was changed to raw material polymer 3 (0.047 mol in terms of MA conversion molar amount calculated from the charging ratio of raw material polymer 3), in the same manner as in Preparation Example 2, 7.5 g of polymer P3 was obtained, in which the structural unit derived from maleic anhydride in raw material polymer 3 was ring-opened with 4-HBA. For the obtained polymer P3, GPC measurement was carried out to measure the weight-average molecular weight and polydispersity of polymer P3. The results are shown in Table 2. Also, by GPC measurement of polymer P3, disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P3 does not contain unreacted monofunctional (meth)acrylic compound.

[0387] (Preparation Example 4) Except that raw material polymer 2 was changed to raw material polymer 4 (0.049 mol in terms of MA conversion molar amount calculated from the charging ratio of raw material polymer 4), in the same manner as in Preparation Example 2, 7.5 g of polymer P4 was obtained, in which the structural unit derived from maleic anhydride in raw material polymer 4 was ring-opened with 4-HBA. For the obtained polymer P4, GPC measurement was carried out to measure the weight-average molecular weight and polydispersity of polymer P4. The results are shown in Table 2. Also, by GPC measurement of polymer P4, disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P4 does not contain unreacted monofunctional (meth)acrylic compound.

[0388] (Preparation Example 5) Except that 10.00 g of raw material polymer 5 (0.034 mol in terms of MA in terms of the composition ratio calculated from the GC measurement of raw material polymer 5) was used instead of raw material polymer 2, in the same manner as in Preparation Example 2, the MA unit of raw material polymer 5 was ring-opened with a monofunctional (meth)acrylic compound to produce polymer P5. For the obtained polymer P5, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P5. The results are shown in Table 2. Also, by GPC measurement of polymer P5, disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P5 does not contain unreacted monofunctional (meth)acrylic compound. Also 13 By 13C-NMR measurement, it was confirmed that polymer P5 has a structure in which the structural unit derived from maleic anhydride was ring-opened with 4-HBA.

[0389] (Preparation Example 6) Except that 60.00 g of raw material polymer 6 (0.213 mol in terms of MA in terms of the composition ratio calculated from the GC measurement of raw material polymer 6) was used instead of raw material polymer 1, in the same manner as in Preparation Example 1, the MA unit of raw material polymer 6 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water to produce polymer P6. For the obtained polymer P6, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P6. The results are shown in Table 2. Also, by GPC measurement of polymer P6, disappearance of the peaks of the used polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P8 does not contain unreacted polyfunctional (meth)acrylic compound nor monofunctional (meth)acrylic compound. Also 13 By 13C-NMR measurement, it was confirmed that polymer P6 has a structure in which the structural unit derived from maleic anhydride was ring-opened with A-TMM-3LM-N, 4-HBA and water.

[0390] (Preparation Example 7) The MA units of the raw material polymer 7 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA) to produce polymer P7. Details are described below. First, 269.15 g of MEK was added to 60 g of the raw material polymer 7 (0.193 mol in terms of MA conversion calculated from the composition ratio determined by GC measurement of the raw material polymer 7) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, followed by reacting at 70°C for 2 hours. Subsequently, 56.27 g (0.390 mol) of 4-HBA was added, and the reaction was carried out at 70°C for 4 hours to prepare a reaction solution. The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. Thereafter, the polymer was purified by the following procedure. · The polymer was reprecipitated with an excess amount of water. · The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated three times. · The operation of washing the polymer powder after the above two washings with an excess amount of water was carried out three times. · The obtained reaction product was dried at 40°C for 16 hours. As described above, polymer P7 was obtained in which the structural units derived from maleic anhydride in the raw material polymer 7 were ring-opened with A-TMM-3LM-N and 4-HBA. By GPC measurement of polymer P7, the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed. Thereby, it was confirmed that the obtained polymer P4 does not contain unreacted (meth)acrylic compounds or (meth)acrylic compounds having no hydroxyl groups. 1 By 1H-NMR measurement, it was confirmed that polymer P7 has a structure ring-opened with A-TMM-3LM-N and 4-HBA.

[0391] (Preparation Example 8) Polymer P8 was obtained in an amount of 5.8 g in the same manner as in Preparation Example 2, except that the raw material polymer 2 was changed to raw material polymer 8 (0.038 mol in terms of maleic anhydride conversion calculated from the composition ratio calculated by GC measurement of raw material polymer 8), and the structural unit derived from maleic anhydride in raw material polymer 8 was ring-opened with 4-HBA. For the obtained polymer P8, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P8. The results are shown in Table 2. Also, by GPC measurement of polymer P8, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed. Thereby, it was confirmed that the obtained polymer P8 does not contain unreacted monofunctional (meth)acrylic compound.

[0392] (Preparation Example 9) Polymer P9 was prepared by ring-opening the MA unit of raw material polymer 9 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water in the same manner as in Preparation Example 1, except that 60.00 g of raw material polymer 9 (0.353 mol in terms of maleic anhydride conversion calculated from the composition ratio calculated by GC measurement of raw material polymer 9) was used instead of raw material polymer 1. For the obtained polymer P9, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P9. The results are shown in Table 2. Also, by GPC measurement of polymer P9, the disappearance of the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed. Thereby, it was confirmed that the obtained polymer P11 does not contain unreacted polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound. Also 13 By C-NMR measurement, it was confirmed that polymer P9 has a structure in which the structural unit derived from maleic anhydride is ring-opened with A-TMM-3LM-N, 4-HBA and water.

[0393] (Preparation Example 10) Instead of raw material polymer 1, 60.00 g of raw material polymer 10 (0.353 moles in terms of maleic anhydride (MA) conversion calculated from the composition ratio determined by GC measurement of raw material polymer 10) was used, and in the same manner as in Preparation Example 1, the MA units of raw material polymer 10 were ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to prepare polymer P10. For the obtained polymer P10, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P10. The results are shown in Table 2. Also, from the GPC measurement of polymer P10, disappearance of the peaks of the trifunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed. Thereby, it was confirmed that the obtained polymer P10 contains neither unreacted trifunctional (meth)acrylic compound nor monofunctional (meth)acrylic compound. Also 13 By C-NMR measurement, it was confirmed that polymer P10 has a structure in which the structural unit derived from maleic anhydride is ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0394] (Preparation Example 11) Instead of raw material polymer 1, 60.00 g of raw material polymer 11 (0.234 moles in terms of maleic anhydride (MA) conversion calculated from the composition ratio determined by GC measurement of raw material polymer 11) was used, and in the same manner as in Preparation Example 1, the MA units of raw material polymer 11 were ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to prepare polymer P11. For the obtained polymer P11, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P11. The results are shown in Table 2. Also, from the GPC measurement of polymer P11, disappearance of the peaks of the trifunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed. Thereby, it was confirmed that the obtained polymer P11 contains neither unreacted trifunctional (meth)acrylic compound nor monofunctional (meth)acrylic compound. Also 13By \(^{13}\)C-NMR measurement, it was confirmed that polymer P11 had a structural unit derived from maleic anhydride and a structure obtained by ring-opening with A-TMM-3LM-N, 4-HBA and water.

[0395] (Preparation Example 12) A polymer P12 was prepared in the same manner as in Preparation Example 2, except that 10.00 g of raw material polymer 12 (0.048 mol in terms of MA calculated from the composition ratio calculated by GC measurement of raw material polymer 12) was used instead of raw material polymer 2, and the MA unit of raw material polymer 12 was ring-opened with a monofunctional (meth)acrylic compound. For the obtained polymer P12, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P12. The results are shown in Table 2. Also, by GPC measurement of polymer P12, the disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P12 did not contain unreacted monofunctional (meth)acrylic compound. Also 13 By \(^{13}\)C-NMR measurement, it was confirmed that polymer P12 had a structural unit derived from maleic anhydride and a structure obtained by ring-opening with 4-HBA.

[0396] (Preparation Example 13) A polymer P13 was prepared in the same manner as in Preparation Example 1, except that 60.00 g of raw material polymer 13 (0.302 mol in terms of MA calculated from the composition ratio calculated by GC measurement of raw material polymer 13) was used instead of raw material polymer 1, and the MA unit of raw material polymer 13 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound and water. For the obtained polymer P13, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P13. The results are shown in Table 2. Also, by GPC measurement of polymer P13, the disappearance of the peaks of the used polyfunctional (meth)acrylic compound and monofunctional (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P13 did not contain unreacted polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound. Also 13 By 13C-NMR measurement, it was confirmed that polymer P13 had a structural unit derived from maleic anhydride and a structure obtained by ring-opening with A-TMM-3LM-N, 4-HBA and water.

[0397] (Preparation Example 14) A polymer P14 was prepared by ring-opening the MA unit of raw material polymer 14 with a monofunctional (meth)acrylic compound in the same manner as in Preparation Example 2, except that 10.00 g of raw material polymer 14 (0.050 mol in terms of MA calculated from the composition ratio calculated by GC measurement of raw material polymer 114) was used instead of raw material polymer 2. For the obtained polymer P14, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P14. The results are shown in Table 2. Also, by GPC measurement of polymer P14, disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P14 did not contain unreacted monofunctional (meth)acrylic compound. Also 13 By 13C-NMR measurement, it was confirmed that polymer P14 had a structural unit derived from maleic anhydride and a structure obtained by ring-opening with 4-HBA.

[0398] (Preparation Example 15) A polymer P15 was prepared by ring-opening the MA unit of raw material polymer 15 with a monofunctional (meth)acrylic compound in the same manner as in Preparation Example 1, except that 10.00 g of raw material polymer 15 (0.046 mol in terms of MA calculated from the composition ratio calculated by GC measurement of raw material polymer 15) was used instead of raw material polymer 2. For the obtained polymer P15, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P15. The results are shown in Table 2. Also, by GPC measurement of polymer P15, disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P15 did not contain unreacted monofunctional (meth)acrylic compound. Also 13By \(^{13}\)C-NMR measurement, it was confirmed that polymer P15 had a structural unit derived from maleic anhydride and a structure in which the ring was opened with 4-HBA.

[0399] (Preparation Example 16) Except that 60.00 g of raw material polymer 16 (0.298 mol in terms of maleic anhydride calculated from the composition ratio calculated by GC measurement of raw material polymer 16) was used instead of raw material polymer 1, in the same manner as in Preparation Example 1, the MA unit of raw material polymer 16 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to prepare polymer P16. For the obtained polymer P16, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P16. The results are shown in Table 2. Also, by GPC measurement of polymer P16, disappearance of the peaks of the trifunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed. Thereby, it was confirmed that the obtained polymer P16 did not contain unreacted trifunctional (meth)acrylic compound or monofunctional (meth)acrylic compound. Also 13 By \(^{13}\)C-NMR measurement, it was confirmed that polymer P16 had a structural unit derived from maleic anhydride and a structure in which the ring was opened with A-TMM-3LM-N, 4-HBA, and water.

[0400] (Preparation Example 17) Except that 10.00 g of raw material polymer 17 (0.049 mol in terms of maleic anhydride calculated from the composition ratio calculated by GC measurement of raw material polymer 17) was used instead of raw material polymer 2, in the same manner as in Preparation Example 2, the MA unit of raw material polymer 17 was ring-opened with a monofunctional (meth)acrylic compound to prepare polymer P17. For the obtained polymer P17, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P17. The results are shown in Table 2. Also, by GPC measurement of polymer P17, disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed. Thereby, it was confirmed that the obtained polymer P17 did not contain unreacted monofunctional (meth)acrylic compound. Also 13 By 13C-NMR measurement, it was confirmed that polymer P17 had a structural unit derived from maleic anhydride and a structure in which the ring was opened with 4-HBA.

[0401] (Preparation Example 18) A polymer P16 in which the MA unit of raw material polymer 18 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared in the same manner as in Preparation Example 7, except that 60.00 g of raw material polymer 18 (0.297 mol in terms of MA calculated from the composition ratio calculated by GC measurement of raw material polymer 18) was used instead of raw material polymer 7. For the obtained polymer P18, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of polymer P16. The results are shown in Table 2. Also, by GPC measurement of polymer P18, disappearance of the peaks of the trifunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used was confirmed. Thereby, it was confirmed that the obtained polymer P18 did not contain unreacted trifunctional (meth)acrylic compound or monofunctional (meth)acrylic compound. Also 13 By 13C-NMR measurement, it was confirmed that polymer P18 had a structural unit derived from maleic anhydride and a structure in which the ring was opened with A-TMM-3LM-N, 4-HBA, and water.

[0402] (Preparation Example 19) A polymer P19 in which the MA unit of raw material polymer 3 was ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and water was prepared. The details are described below. First, 269.15 g of MEK was added to 60.00 g of raw material polymer 17 (0.297 mol in terms of MA calculated from the composition ratio calculated by GC measurement of raw material polymer 17) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at 70 °C for 2 hours. Next, without post-treating the obtained reaction solution, 1.20 g (0.067 mol) of water was added to this reaction solution and reacted at 70 °C for 2 hours. The obtained reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Then, it was further purified by the following procedure. · The polymer was reprecipitated with an excess amount of water. · The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated 3 times. · The operation of washing the polymer powder after the above two washings with an excess amount of water was performed 3 times. · The obtained reaction product was dried at 40 °C for 12 hours. As described above, the MA unit of the raw material polymer 17 was ring-opened with a trifunctional (meth)acrylic compound and water to produce a polymer P19. For the obtained polymer P19, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of the polymer P19. The results are shown in Table 2. Also, by GPC measurement of the polymer P19, the disappearance of the peak of the polyfunctional (meth)acrylic compound used was confirmed. Thereby, it was confirmed that the obtained polymer P19 does not contain unreacted polyfunctional (meth)acrylic compound. Also 13 By C-NMR measurement, it was confirmed that the polymer P19 has a structure in which the structural unit derived from maleic anhydride is ring-opened with A-TMM-3LM-N and water.

[0403] (Preparation Example 20) The MA unit of the raw material polymer 18 was ring-opened with a monofunctional (meth)acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce a polymer P20. Details are described below. First, 275.02 g of MEK was added to 60 g of raw material polymer 18 (0.297 moles in terms of MA conversion calculated from the composition ratio determined by GC measurement of raw material polymer 18) to prepare a solution. Next, 27.01 g (0.187 moles) of 4-HBA was added to this solution, and then 18.00 g (0.178 moles) of triethylamine was added, followed by reacting at 70 °C for 6 hours. Subsequently, 19.97 g (0.140 moles) of GMA was added and reacted at 70 °C for 4 hours. The prepared reaction solution was diluted with MEK, and the aqueous phase was removed from the reaction solution by treating it with an aqueous formic acid solution and an aqueous citric acid solution. Furthermore, liquid-liquid extraction and then solvent replacement were carried out in the following procedure. · Liquid-liquid extraction: The reaction solution was diluted with MEK, and then a water / methanol mixed solvent was added and treated to remove the aqueous phase from the reaction solution. Subsequently, the same operation was performed one more time. · Solvent replacement: The obtained reaction mixture was subjected to solvent removal at 50 °C under reduced pressure using a rotary evaporator. It was confirmed that the solid content concentration of the polymer solution reached 27 ± 2 mass% as measured by a heating drying type moisture meter, and the solvent removal operation was interrupted. Thereafter, PGMEA was added so that the solid content concentration became 18 mass%, and the mixture was stirred until it became uniform. The same operation was performed to remove the solvent at 50 °C under reduced pressure, and after adjusting the solid content concentration to 27 ± 2 mass% as measured by a heating drying type moisture meter, the operation of adding PGMEA so that the solid content concentration became 18 mass% and stirring until it became uniform was repeated two more times. Thereafter, the operation of removing the solvent or adding PGMEA so that the solid content concentration became 30 ± 3 mass% and stirring until it became uniform was performed. By the above operations, the solvent used in the reaction was removed and replaced with PGMEA. Subsequently, it was further purified by the following reprecipitation method. · The polymer was reprecipitated with an excessive amount of toluene. · The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of toluene was repeated twice. · The operation of washing the polymer powder after the above two washings with an excessive amount of water was performed three times. · The obtained reaction product was dried at 40 °C for 12 hours. As a result of the above, the structural unit derived from maleic anhydride in the raw polymer 18 was ring-opened with 4-HBA, and polymer P20 was obtained by reacting with GMA. The weight average molecular weight and polydispersity of the obtained polymer P20 were measured by GPC measurement. The results are shown in Table 2. Furthermore, the disappearance of peaks of the polyfunctional (meth)acrylic compound and monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P20, which confirmed that the obtained polymer P20 did not contain any unreacted polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P20 had a structure in which the maleic anhydride-derived structural unit of raw material polymer 18 was ring-opened with 4-HBA, and a structure in which GMA was introduced.

[0404] Figure 5 shows the structure of polymer P20. 1 The H-NMR chart of polymer P20 in FIG. 1 In addition to the peak corresponding to the 3H of the acryloyl group (-CH=CH2) at 5.8-6.7 ppm shown in the H-NMR chart, peaks corresponding to the 2H of the methacryloyl group (-C(CH3)=CH2 (CH2 of -C(CH3)=CH2) appeared at 5.6-5.8 ppm and 6.0-6.1 ppm, indicated by x. In the GPC measurement of polymer P20, no peaks were observed for the unreacted trifunctional (meth)acrylic compound (A-TMM-3LM-N), monofunctional (meth)acrylic compound (4-HBA), or epoxy group-containing (meth)acrylic compound (GMA), indicating that the acryloyl group and the methacryloyl group derived from GMA were introduced into the polymer.

[0405] Also, in the GPC measurement of the reaction solution before and after the ring-opening reaction and before and after the GMA addition reaction, the peaks derived from the trifunctional (meth)acrylic compound (A-TMM-3LM-N) and the monofunctional (meth)acrylic compound (4-HBA) decreased before and after the ring-opening reaction, and the peak derived from GMA decreased before and after the GMA addition reaction. This also indicates that A-TMM-3LM-N, 4-HBA, and GMA were introduced into the polymer.

[0406] Also 13 By 13C-NMR measurement, it was confirmed that the polymer P20 had a structure in which the maleic anhydride-derived structural unit of the raw material polymer 18 was ring-opened with A-TMM-3LM-N and 4-HBA, and a structure in which GMA was introduced.

[0407] (Preparation Example 21) A polymer P21 was prepared in the same manner as in Preparation Example 2, except that 10.00 g of the raw material polymer 19 (0.043 mol in terms of maleic anhydride, calculated from the composition ratio determined by GC measurement of the raw material polymer 19) was used instead of the raw material polymer 2, and the MA unit of the raw material polymer 19 was ring-opened with a monofunctional (meth)acrylic compound. For the obtained polymer P21, GPC measurement was carried out to measure the weight average molecular weight and polydispersity of the polymer P21. The results are shown in Table 2. Also, by GPC measurement of the polymer P21, the disappearance of the peak of the used monofunctional (meth)acrylic compound was confirmed. This confirmed that the obtained polymer P21 did not contain unreacted monofunctional (meth)acrylic compound. Also 13 By 13C-NMR measurement, it was confirmed that the polymer P21 had a structure in which the structural unit derived from maleic anhydride was ring-opened with 4-HBA.

[0408] (Physical Property Evaluation) The acid value and double bond equivalent of each polymer P prepared in Preparation Examples 1 to 21 were measured by the following methods.

[0409] (Acid Value) The acid value of the polymer was measured by the following method. About 50 mg of the polymer and about 5 mg of dimethyl terephthalate as an internal standard substance were weighed and dissolved in DMSO-d6. For this solution, using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL Ltd.) 1 1H-NMR measurement was performed. 1 Based on the integration value of the 4H peak (around 8.1 ppm) of the phenyl group of dimethyl terephthalate, which is the internal standard for 1H-NMR measurement, the amount of carboxy groups (-COOH) in the polymer is determined from the integration value of the H peak (around 12.4 ppm) of the carboxy groups. And the acid value (mgKOH / g) can be calculated from that amount. The larger the value of the acid value, the more carboxy groups there are per unit mass of the polymer. The results are shown in Table 2. Since the acid value is 50 gKOH / g or more, it can be considered that carboxy groups necessary for the polymer to have sufficient developability are present in the polymer.

[0410] (Double bond equivalent) The double bond equivalent of the polymer was measured by the following method. Similar to the above method for measuring the acid value, 1 1H-NMR measurement was performed. From the integration ratio of the signal (5.6 - 5.8 ppm, 3H) derived from the acryloyl group and the signal (8.1 ppm, 4H) of the phenyl group of the internal standard substance in the obtained spectrum chart, the amount of acryloyl groups (mol / g) in the polymer was calculated, and from the integration ratio of the signal (5.6 - 5.8 ppm, 2H) derived from the methacryloyl group and the signal (8.1 ppm, 4H) of the phenyl group of the internal standard substance, the amount of methacryloyl groups (mol / g) in the polymer was calculated. Here, the signal derived from the methacryloyl group at 6.0 - 6.1 ppm is minute and overlaps with the signal of the acryloyl group, so it was calculated as the signal of the acryloyl group. The double bond amount (mol / g) was calculated from the sum of the calculated amount of acryloyl groups (mol / g) and methacryloyl groups (mol / g) in the polymer, and from the double bond amount, the double bond equivalent (g / mol) was calculated. The results are shown in Table 2. The smaller the value of the double bond equivalent, the more C=C double bonds there are per unit mass of the polymer.

[0411] For polymers P2 to P5, P7, P12, P14, P15, 17, 18, 20, and 21 1 The introduction ratio (molar ratio) of the compound reacted with the raw material polymer in the overall structure was calculated by 1H-NMR measurement. The results are shown in Table 2.

[0412] [Table 2] [Table 3]

[0413] (Examples 1 to 17, Comparative Examples 1 to 4) In each of the examples and comparative examples, a resin composition was prepared and evaluated for the following items. <Evaluation> [Alkali dissolution rate of the resin composition] Polymers P1 to P21 obtained in Preparation Examples 1 to 21 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1 to 21 with a solid content concentration of 30% by mass. Next, resin compositions 1 to 21 were spin-coated on a wafer, PGMEA was dried, and then pre-baked at a temperature of 100°C for 2 minutes to prepare a resin film with a film thickness of about 2 μm. This resin film was immersed, together with the wafer, in a 2% aqueous sodium carbonate solution at a temperature of 23°C, and the dissolution rate of the resin film was measured. The dissolution rate was calculated by measuring the time until the resin film dissolved and the interference pattern disappeared by visually observing the immersed wafer, and dividing the film thickness by that time. The results are shown in Table 3. If the alkali dissolution rate is 50 nm / s or more, it can be used without problems as a photosensitive material. If it is 100 nm / s or more, it can be regarded as having good developability. If it is 200 nm / s or more, it can be regarded as better. If it is 500 nm / s or more, it can be regarded as particularly good.

[0414] [Softening point of the raw material polymer] The softening points of starting polymers 1 to 19 were measured by the following method. First, 0.1 to 1.0 mg of the polymer to be measured (starting polymers 1 to 19) was placed in an aluminum sample pan, and the softening point was measured using a differential thermal analyzer (manufactured by Hitachi High-Tech Science Corporation, "EXSTAR TMA / SS6100") under a nitrogen atmosphere. The measurement mode was compression, the load was 30 mN, and the temperature was raised from 30 °C to 200 °C at a rate of 3 °C / min. When the sample softened due to heating, the sample deformed and was detected as the displacement amount (μm). The intersection of the extension of the straight line part without displacement on the low-temperature side or the tangent line of the minimum part of the displacement rate and the tangent line of the maximum part of the displacement rate was defined as the softening point. The measurement results of the softening points are shown in Table 1. If the softening point of the starting polymer is 158 °C or lower, it can be said that the softening point is low; if it is 120 °C or lower, it can be said that the softening point is lower; if it is 100 °C or lower, it can be said that the softening point is particularly lower; if it is 80 °C or lower, it can be said that the softening point is even more particularly lower.

[0415] [Melting point of starting polymer] The melting points of starting polymers 1 to 19 were measured by the following method. First, 1 to 2 mg of the polymer to be measured (starting polymers 1 to 19) was placed in an aluminum sample pan, and while observing the image, the temperature was raised from 30 °C at a rate of 10 °C / min using a differential thermal analyzer (manufactured by Hitachi High-Tech Science Corporation, "STA7200RV") under a nitrogen atmosphere. The temperature at which the melting of the sample started was visually confirmed and defined as the melting point. If the melting point of the starting polymer is 180 °C or lower, it can be said that the melting point is low; if it is 160 °C or lower, it can be said that the melting point is lower; if it is 140 °C or lower, it can be said that the melting point is particularly lower; if it is 100 °C or lower, it can be said that the melting point is even more particularly lower. The results are shown in Table 1.

[0416] [Softening point of polymer P] The softening points of polymers P1 to P21 obtained in Preparation Examples 1 to 21 were measured by the following method. First, 0.1 - 1.0 mg of the polymer to be measured (polymers P1 - P21) was placed in an aluminum sample pan, and the softening point was measured using a differential thermal analyzer (manufactured by Hitachi High - Technologies Corporation, "EXSTAR TMA / SS6100") under a nitrogen atmosphere. The measurement mode was compression, the load was 30 mN, and the temperature was raised from 30°C to 200°C at a rate of 3°C / min. When the sample softened upon heating, the sample deformed and was detected as the displacement amount (μm). The intersection of the extension of the straight - line part with no displacement on the low - temperature side or the tangent line of the minimum part of the displacement rate and the tangent line of the maximum part of the displacement rate was defined as the softening point. The results are shown in Table 2. If the softening point of polymer P is 100°C or lower, it can be said that the softening point is low; if it is 80°C or lower, it can be said that the softening point is lower; if it is 60°C or lower, it can be said that the softening point is particularly lower; if it is 40°C or lower, it can be said that the softening point is even more particularly lower.

[0417] [Melting point of polymer P] The melting points of polymers P1 - P21 obtained in Preparation Examples 1 - 21 were measured by the following method. First, 1 - 2 mg of the polymer to be measured (polymers P1 - P21) was placed in an aluminum sample pan, and under a nitrogen atmosphere, using a differential thermal analyzer (manufactured by Hitachi High - Technologies Corporation, "STA7200RV"), while observing the image, the temperature was raised from 30°C at a rate of 10°C / min. The temperature at which the melting of the sample started was visually confirmed and defined as the melting point. The results are shown in Table 2. If the melting point of polymer P is 130°C or lower, it can be said that the melting point is low; if it is 110°C or lower, it can be said that the melting point is lower; if it is 90°C or lower, it can be said that the melting point is particularly lower; if it is 70°C or lower, it can be said that the melting point is even more particularly lower.

[0418] [Softening point of the cured product of the photosensitive resin composition] The softening points of the photosensitive resin compositions prepared from polymers P1 - P21 obtained in Preparation Examples 1 - 21 were measured by the following method. First, a photosensitive resin composition in which the following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) was obtained so that the total solid content concentration became 30% by mass. · Polymers P1 to P21 (Polymers P obtained in Preparation Examples 1 to 21 respectively): 100 parts by mass · Photoinitiator (Irgacure OXE01 manufactured by BASF): 5 parts by mass The obtained photosensitive resin composition was poured into a container with dimensions of 2 cm × 2 cm and a height of 5 mm, which was pasted with a Teflon adhesive tape (Nitoflon adhesive tape, No. 903UL (thickness 0.08 mm, width 25 mm, length 10 mm), Nitto Denko Corporation) without gaps. After that, it was vacuum dried at 40°C for 16 hours to remove the solvent. Then, it was exposed to g + h + i rays with an exposure amount of 100 mJ / cm 2 After exposure, the cured product was peeled off from the Teflon adhesive tape to obtain a cured product of the photosensitive resin composition. 0.1 to 1.0 mg of the cured product of the photosensitive resin composition to be measured was placed in an aluminum sample pan, and the softening point was measured using a differential thermal analyzer (manufactured by Hitachi High-Tech Science Corporation, "EXSTAR TMA / SS6100") under a nitrogen atmosphere. The measurement mode was compression, the load was 30 mN, and the temperature was raised from 30°C to 200°C at a heating rate of 1°C / min. When the sample softened due to heating, the sample deformed and was detected as the displacement amount (μm). The intersection of the extension of the straight part without displacement on the low-temperature side or the tangent of the minimum part of the displacement rate and the tangent of the maximum part of the displacement rate was defined as the softening point. Table 3 shows the evaluation results of the softening point of the cured product of the photosensitive resin composition evaluated according to the following criteria. A: Softening point is lower than 100°C B: Softening point is 100°C or higher If the softening point of the cured product of the photosensitive resin composition is lower than 100°C, it can be said that the softening point is low and the pattern formability is good.

[0419] [Evaluation of the sensitivity of the photosensitive resin composition (exposure amount at which the residual film rate is 90% or more)] First, a photosensitive resin composition in which the following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) was obtained so that the total solid content concentration became 30% by mass. · Polymers P1 to P21 (Polymers P of Preparation Examples 1 to 21 respectively): 100 parts by mass · Multifunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by mass · Photoinitiator (Irgacure OXE01, manufactured by BASF): 5 parts by mass · Adhesion promoter (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by mass · Surfactant (F-556, manufactured by DIC Corporation): 0.5 part by mass

[0420] The obtained photosensitive resin composition was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100 °C for 120 seconds to obtain a thin film A with a thickness of about 3.0 μm (±0.3 μm). This thin film A was irradiated with g+h+i rays at an exposure dose of 100 mJ / cm 2 through a photomask having a gradation with a light shielding rate of 1 to 100% using a g+h+i ray mask aligner (PLA-501F) manufactured by Canon. After exposure, the thin film was developed in a 2.0 mass% aqueous sodium carbonate solution at 23 °C for 60 seconds (immersed together with the wafer), and thus thin films B exposed and developed at each exposure dose of 1 to 100 mJ / cm 2 were obtained. From the film thicknesses of the thin film A and the thin film B obtained by the above method, the residual film ratio was calculated from the following formula. Residual film ratio (%) = (film thickness of thin film B at each exposure dose / film thickness of thin film A) × 100 And the exposure dose at which the residual film ratio becomes 90% or more was defined as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. If the exposure dose at which the residual film ratio becomes 90% or more is 50 mJ / cm 2 or less, it can be used without problems as a photosensitive composition. If it is 30 mJ / cm 2 or less, it can be regarded as having good sensitivity. If it is 20 mJ / cm 2 or less, it can be regarded as better. Furthermore, if it is 15 mJ / cm 2 or less, it can be regarded as particularly good.

[0421] [Alkali dissolution rate of photosensitive resin composition (2.0 mass% sodium carbonate aqueous solution)] The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on a wafer, dried with PGMEA, and pre-baked at a temperature of 100 °C for 2 minutes to produce a resin film with a film thickness of about 2 μm. This resin film was immersed in a 2% sodium carbonate aqueous solution at a temperature of 23 °C together with the wafer, and the dissolution rate of the resin film was measured. The dissolution rate was calculated by observing the immersed wafer visually and measuring the time until the resin film dissolved and the interference pattern disappeared, and then dividing the film thickness by that time. The results are shown in Table 3. If the alkali dissolution rate is 500 nm / s or more, it can be used without problems as a photosensitive material. If it is 800 nm / s or more, the developability can be considered good. If it is 1500 nm / s or more, it can be considered better, and if it is 2,000 nm / s or more, it can be considered particularly good.

[0422] [Yellow index] The photosensitive resin composition prepared in the above sensitivity evaluation 1 was spin-coated on Eagle XG glass (manufactured by Corning, thickness 0.5 mm), baked on a hot plate at 100 °C for 120 seconds to obtain a thin film with a thickness of about 3.0 μm (±0.1 μm). This thin film was exposed to g+h+i rays with an exposure dose of 100 mJ / cm 2 using a g+h+i line mask aligner (PLA-600F) manufactured by Canon. After exposure, the thin film was developed in a 2.0 mass% sodium carbonate aqueous solution at 23 °C for 60 seconds (immersed together with the wafer) to obtain a thin film exposed and developed with an exposure dose of 100 mJ / cm 2 . The thin film was heat-treated at 230 °C for 30 minutes in air. After cooling the thin film in room-temperature air, the thin film was heat-treated again at 230 °C for 30 minutes in air. The same operation was repeated, and the heat treatment in air was performed a total of 3 times for 30 minutes. The yellow index (YI) of the thin film obtained by the above method was measured three times while changing the measurement location using a color difference meter CR-5 (manufactured by Konica Minolta), and the average value was taken as the value of YI. The measurement type was transmission measurement, and for the 100% calibration, uncoated Eagle XG glass (manufactured by Corning, thickness 0.5 mm) was used. The results are shown in Table 3. If the yellow index is 2.00 or less, it can be used without problems as a photosensitive material. If it is 1.50 or less, it can be considered to have good heat discoloration resistance. If it is 1.30 or less, it can be considered to have better heat discoloration resistance. If it is 1.10 or less, it can be considered to have particularly better heat discoloration resistance.

[0423] The results of the developability evaluation and the sensitivity evaluation are shown in Table 3.

[0424]

Table 4

Table 5

[0425] The polymers P5 to P21 obtained from the raw materials polymers 5 to 19 having a softening point of 20°C or higher and 158°C or lower had a low softening point of 0°C or higher and 100°C or lower. The photosensitive resin compositions of Examples 1 to 17 containing polymers P5 to P21 have a low softening point of less than 100°C, and thus are likely to melt due to heat during curing, and it is predicted that the processability and pattern formability in photolithography processing are good. Also, the photosensitive resin compositions containing the polymers of Examples 1 to 17 had a well-balanced alkali solubility, sensitivity, and heat discoloration resistance. The photosensitive resin compositions of Examples 2, 3, 5 to 7, 9, 12, 14, and 15, which contain a polymer having a structure ring-opened with a polyfunctional (meth)acrylic compound, had a lower exposure dose at which the residual film ratio became 90% or more, and were particularly excellent in sensitivity. Further, the photosensitive resin compositions of Examples 2, 3, 5 to 7, 9, and 12, which contain a polymer having a structure ring-opened with both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound, had a lower exposure dose at which the residual film ratio became 90% or more, and were particularly excellent in sensitivity.

[0426] <Fabrication of Color Filter / Spacer> For the photosensitive resin compositions prepared in Examples 1 to 17, a colored photosensitive resin composition was further prepared by adding an appropriate amount of a pigment dispersion liquid NX-061 (manufactured by Dainichi Seika Kogyo Co., Ltd., green). By forming a film of this on a substrate and performing exposure, alkali development treatment, etc., a green color filter could be formed. Also, as the pigment dispersion liquid, instead of NX-061, NX-053 (blue), NX-032 (red), etc. manufactured by the same company were used, and blue or red color filters could be formed.

[0427] <Fabrication of Black Matrix / Black Bank / Black Spacer> For the photosensitive resin compositions prepared in Examples 1 to 17, a black photosensitive resin composition was further prepared by adding an appropriate amount of a carbon black dispersion liquid NX-595 (manufactured by Dainichi Seika Kogyo Co., Ltd.). By forming a film of this on a substrate and performing exposure, alkali development treatment, etc., a black matrix / black bank / black spacer could be formed.

Explanation of Reference Numerals

[0428] 10 Substrate 11 Black Matrix 12 Color Filter 13 Protective Film 14 Transparent Electrode Layer

Claims

1. A first structural unit derived from maleic anhydride, which contains a structural unit represented by formula (8) and / or a structural unit represented by formula (9), or a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (5) and / or a structural unit represented by formula (6), the first structural unit, A polymer containing, as a main backbone, one second structural unit selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), a structural unit represented by formula (IN), a structural unit represented by formula (AK), and a structural unit represented by formula (CA), When the first structural unit contains a structural unit represented by formula (8) and / or a structural unit represented by formula (9), The structural unit represented by formula (8) is 0.5 mol% or more and 12 mol% or less based on all the structural units of the polymer, The structural unit represented by formula (9) is 0.5 mol% or more and 12 mol% or less based on all the structural units of the polymer, When the first structural unit contains a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (5) and / or a structural unit represented by formula (6), The structural unit represented by formula (1) is 1 mol% or more and 18 mol% or less based on all the structural units of the polymer, The structural unit represented by formula (2) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer, The structural unit represented by formula (5) is 1 mol% or more and 9 mol% or less based on all the structural units of the polymer, The structural unit represented by formula (6) is 1 mol% or more and 8 mol% or less based on all the structural units of the polymer, When the second structural unit contains a structural unit represented by formula (NB), The structural unit represented by formula (NB) is 35 mol% or more and 60 mol% or less based on all the structural units of the polymer, When the second structural unit contains a structural unit represented by the formula (ST), The structural unit represented by the formula (ST) is 35 mol% or more and 60 mol% or less based on all the structural units of the polymer, When the second structural unit contains a structural unit represented by the formula (IN), The structural unit represented by the formula (IN) is 7 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the second structural unit contains a structural unit represented by the formula (AK), The structural unit represented by the formula (AK) is 5 mol% or more and 50 mol% or less based on all the structural units of the polymer, When the second structural unit contains a structural unit represented by the formula (CA), The structural unit represented by the formula (CA) is 5 mol% or more and 25 mol% or less based on all the structural units of the polymer, The softening point of the polymer measured under the following (Condition 1) is 0 °C or higher and 100 °C or lower, (Condition 1: 0.1 to 1.0 mg of the polymer is placed in an aluminum sample pan, and using a differential thermal analyzer under a nitrogen atmosphere, the measurement mode is compression, the load is 30 mN, and the temperature is raised from 30 °C to 200 °C at a heating rate of 3 °C / min. The amount by which the polymer softens and deforms upon heating is detected as the displacement amount (μm), and the intersection of the extension of the straight line portion without displacement on the low temperature side or the tangent line at the minimum portion of the displacement rate and the tangent line at the maximum portion of the displacement rate is defined as the softening point.) [Chemical Formula 1] [Chemical Formula 2] In Formula (8) and Formula (9), Z is a (meth)acryloyl group, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, R ２１ and R ２２ are hydrogen atoms, R ｐis at least one selected from the group represented by formula (1b), the group represented by formula (1c), and the group represented by formula (1d), R ｓ is the group represented by formula (2a), [Chemical Formula 3] [Chemical Formula 4] In formula (1) and formula (2), R ２１ and R ２２ are hydrogen atoms, R ｐ is at least one selected from the group represented by formula (1b), the group represented by formula (1c), and the group represented by formula (1d), R ｓ is the group represented by formula (2a), [Chemical Formula 5] [Chemical Formula 6] In formula (5) and formula (6), Z is a (meth)acryloyl group, Q is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, R ２１ and R ２２ are hydrogen atoms, [Chemical Formula 7] In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different, X １ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and a plurality of Xs １ may be the same or different, X １ ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z' - (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X ２ is a group obtained by removing (k + 1) hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms, 【Chemical Formula 8】 In formula (1c), k, R, X １ and X ２ are, respectively, R, k, X in formula (1b) １ and X ２ and have the same meaning. A plurality of Rs may be the same as or different from each other, and a plurality of Xs １ may be the same as or different from each other, X ３ is a single bond or a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms, X ６ is an alkylene group having 1 to 6 carbon atoms, 【Chemical Formula 9】 In formula (1d), n is an integer from 2 to 5, R is independently a hydrogen atom or a methyl group, 【Chemical Formula 10】 In formula (2a), X １０ is an alkylene group having 1 to 6 carbon atoms, and R is a hydrogen atom or a methyl group, 【Chemical Formula 11】 In formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a １ is 0, 1 or 2, 【Chemical Formula 12】 In formula (ST), R ４０ , R ４１ and R ４２ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４３ is each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, [Chemical Formula 13] In formula (IN), R ６１ ~R ６８ is each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, [Chemical Formula 14] In formula (AK), R ７１ , R ７２ , R ７３ and R ７４ at least one of which is a linear or branched alkyl group having 3 to 30 carbon atoms, and the rest of R ７１ , R ７２ , R ７３ and R ７４ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, [Chemical Formula 15] In formula (CA), X ５１ is a single bond or a linear or branched alkylene group having 1 to 30 carbon atoms, When X ５１ is a single bond, at least one of R ５１ , R ５２ and R ５３ is a linear or branched alkyl group having 2 to 30 carbon atoms, and the rest of R ５１ , R ５２ and R ５３ are a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, When X ５１ is a linear or branched alkylene group having 1 to 30 carbon atoms, R ５１ , R ５２ and R ５３ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, Polymer.

2. The polymer according to claim 1, Further comprising one third structural unit selected from the structural unit represented by formula (MI) and the structural unit represented by formula (AD), 【Chemical 16】 In formula (MI), R ３１ is a hydrogen atom or an organic group having 1 to 30 carbon atoms, R ３２ and R ３３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, 【Chemical 17】 In formula (AD), R １１ and R １２ are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, R １３ and R １４ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, When the third structural unit contains the structural unit represented by the formula (MI), The structural unit represented by the formula (MI) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the third structural unit contains the structural unit represented by the formula (AD), The structural unit represented by the formula (AD) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer.

3. The polymer according to claim 1, The first structural unit derived from maleic anhydride further contains a structural unit represented by formula (MA), The structural unit represented by the formula (MA) is 10 mol% or more and 30 mol% or less based on all the structural units of the polymer, 【Chemical 18】 In formula (MA), R ２１ and R ２２ are hydrogen atoms.

4. The polymer according to claim 1, The polymer has a structure represented by the formula (P2), [Chemical Formula 19] In the formula (P2), n is an integer from 1 to 6, p and q represent the molar contents of the structural units A and B contained in each polymer chain within n [ ]. p and q may be the same or different for each polymer chain within n [ ]. p + q = 1, p is 0 or more, and q is 0 or more. Regarding the molar contents of each structural unit A and B contained in the polymer as p ｔ and q ｔ respectively, then p ｔ + q ｔ = 1, p ｔ is greater than 0, and q ｔ is greater than 0. X is hydrogen or an organic group having 1 to 30 carbon atoms. Y is a monofunctional or polyfunctional (from bifunctional to hexafunctional) organic group having 1 to 30 carbon atoms derived from a thiol group-containing compound. A represents one of the second structural units selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), the structural unit represented by the formula (IN), the structural unit represented by the formula (AK), and the structural unit represented by the formula (CA). B contains the first structural unit derived from maleic anhydride. A polymer in which a plurality of As and Bs may be the same or different from each other.

5. The polymer according to claim 2, wherein the polymer has a structure represented by the formula (P3), [Chemical Formula 20] In the formula (P3), n is an integer from 1 to 6, p, q, and r represent the molar contents of the structural units A, B, and C contained in each polymer chain within n [ ]. p, q, and r may be the same or different for each polymer chain within the n [ ], p + q + r = 1, p is 0 or more, q is 0 or more, and r is 0 or more, The molar content ratios of each structural unit A, B, and C contained in the polymer are p ｔ , q ｔ and r ｔ respectively. Then, p ｔ + q ｔ + r ｔ = 1, p ｔ is greater than 0, q ｔ is greater than 0, r ｔ is greater than 0, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monofunctional or polyfunctional (from 2 to 6 functional groups) organic group having 1 to 30 carbon atoms derived from a thiol group-containing compound, A represents one of the second structural units selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), the structural unit represented by the formula (IN), the structural unit represented by the formula (AK), and the structural unit represented by the formula (CA), B contains the first structural unit derived from maleic anhydride, C represents one of the third structural units selected from the structural unit represented by the formula (MI) and the structural unit represented by the formula (AD), A plurality of As, Bs, and Cs may be the same or different, a polymer.

6. The first structural unit derived from maleic anhydride, which contains the structural unit represented by the formula (1), and the first structural unit derived from maleic anhydride, A polymer containing, as a main backbone, one of the second structural units selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), the structural unit represented by the formula (IN), the structural unit represented by the formula (AK), and the structural unit represented by the formula (CA), The structural unit represented by the formula (1) is 1 mol% or more and 18 mol% or less with respect to all the structural units of the polymer, When the second structural unit includes the structural unit represented by the formula (NB), the structural unit represented by the formula (NB) is 35 mol% or more and 60 mol% or less based on all the structural units of the polymer, When the second structural unit includes the structural unit represented by the formula (ST), the structural unit represented by the formula (ST) is 35 mol% or more and 60 mol% or less based on all the structural units of the polymer, When the second structural unit includes the structural unit represented by the formula (IN), the structural unit represented by the formula (IN) is 7 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the second structural unit includes the structural unit represented by the formula (AK), the structural unit represented by the formula (AK) is 5 mol% or more and 50 mol% or less based on all the structural units of the polymer, When the second structural unit includes the structural unit represented by the formula (CA), the structural unit represented by the formula (CA) is 5 mol% or more and 25 mol% or less based on all the structural units of the polymer, The softening point of the polymer measured under the following (Condition 1) is 0 °C or higher and 100 °C or lower, (Condition 1: Put 0.1 to 1.0 mg of the polymer into an aluminum sample pan, use a differential thermal analyzer under a nitrogen atmosphere, the measurement mode is compression, the load is 30 mN, and heat up at a heating rate of 3 °C / min in the range from 30 °C to 200 °C. Detect the amount by which the polymer softens and deforms upon heating as the displacement amount (μm), and take the intersection of the extension of the straight line part without displacement on the low temperature side or the tangent line of the minimum part of the displacement rate and the tangent line of the maximum part of the displacement rate as the softening point) [Chemical Formula 21] In formula (1), R ２１ and R ２２ are hydrogen atoms, R ｐis at least one selected from the group consisting of a group represented by formula (1b), a group represented by formula (1c), and a group represented by formula (1d), [Chemical Formula 22] In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different, X １ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and a plurality of Xs １ may be the same or different, X １ ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z' - (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X ２ is a group obtained by removing (k + 1) hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms, [Chemical Formula 23] In formula (1c), k, R, X １ and X ２ are, respectively, the same as R, k, X １ and X ２ in formula (1b), and a plurality of Rs may be the same or different from each other, and a plurality of Xs １ may be the same or different from each other, X ３ is a single bond or a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms, X ６ is an alkylene group having 1 to 6 carbon atoms, [Chemical Formula 24] In formula (1d), n is an integer from 2 to 5, R is independently a hydrogen atom or a methyl group, [Chemical Formula 25] In formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a １ is 0, 1, or 2, [Chemical Formula 26] In formula (ST), R ４０ , R ４１ and R ４２ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４３ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, [Chemical Formula 27] In formula (IN), R ６１ to R ６８ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, [Chemical Formula 28] In formula (AK), at least one of R ７１ , R ７２ , R ７３ and R ７４ is a linear or branched alkyl group having 3 to 30 carbon atoms, and the remainder of R ７１ , R ７２ , R ７３ and R ７４ are each independently a hydrogen atom, or a linear or branched alkyl group having 1 to 30 carbon atoms, [Chemical Formula 29] In formula (CA), X ５１ is a single bond, or a linear or branched alkylene group having 1 to 30 carbon atoms, When X ５１ is a single bond, at least one of R ５１ , R ５２ and R ５３ is a linear or branched alkyl group having 2 to 30 carbon atoms, and R ５１ , R ５２ and R ５３ The remainder is a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, X ５１ When is a linear or branched alkylene group having 1 to 30 carbon atoms, R ５１ R, ５２ and R ５３ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, A polymer (however, The structural unit represented by the above formula (NB), The structural unit represented by the formula (AD), At least one structural unit selected from the structural unit represented by the formula (1) and the structural unit represented by the formula (2), A polymer containing, [Chemical Formula 30] In the formula (1), R ｐ is a group having two or more (meth)acryloyl groups, R ２１ and R ２２ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, [Chemical Formula 31] In the formula (2), R ｓ is a group having one (meth)acryloyl group, R ２１ and R ２２ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, [Chemical Formula 32] In the formula (AD), R １１ and R １２ are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, R １３ and R １４ are hydrogen atoms (excluding polymers).

7. The polymer according to claim 6, Further comprising one third structural unit selected from the structural unit represented by the formula (MI) and the structural unit represented by the formula (AD), 【Chemical Formula 33】 In formula (MI), R ３１ is a hydrogen atom or an organic group having 1 to 30 carbon atoms, R ３２ and R ３３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, 【Chemical Formula 34】 In formula (AD), R １１ and R １２ are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, R １３ and R １４ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, When the third structural unit contains the structural unit represented by the formula (MI), the structural unit represented by the formula (MI) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the third structural unit contains the structural unit represented by the formula (AD), the structural unit represented by the formula (AD) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer. Polymer.

8. The polymer according to claim 6, the first structural unit derived from maleic anhydride further includes at least one structural unit selected from the structural unit represented by formula (8), the structural unit represented by formula (9), the structural unit represented by formula (5), and the structural unit represented by formula (6), When the first structural unit contains the structural unit represented by the formula (8), the structural unit represented by the formula (8) is 0.5 mol% or more and 12 mol% or less based on all the structural units of the polymer, When the first structural unit contains the structural unit represented by the formula (9), the structural unit represented by the formula (9) is 0.5 mol% or more and 12 mol% or less based on all the structural units of the polymer, When the first structural unit contains the structural unit represented by the formula (5), The structural unit represented by the formula (5) is 1 mol% or more and 9 mol% or less based on all the structural units of the polymer, When the first structural unit contains the structural unit represented by the formula (6), The structural unit represented by the formula (6) is 1 mol% or more and 8 mol% or less based on all the structural units of the polymer, 【Chemical Formula 35】 【Chemical Formula 36】 In the formula (8) and the formula (9), Z is a (meth)acryloyl group, Q is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, R ２１ and R ２２ are hydrogen atoms, R ｐ is at least one selected from the group consisting of the group represented by the formula (1b), the group represented by the formula (1c), and the group represented by the formula (1d), R ｓ is a group represented by the formula (2a), 【Chemical Formula 37】 In the formula (2a), X １０ is an alkylene group having 1 to 6 carbon atoms, and R is a hydrogen atom or a methyl group, 【Chemical Formula 38】 【Chemical Formula 39】 In the formula (5) and the formula (6), Z is a (meth)acryloyl group, Q is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, R ２１ and R ２２ are hydrogen atoms, a polymer.

9. The polymer according to claim 6, wherein the first structural unit derived from maleic anhydride includes a structural unit represented by formula (2), 【Chemical formula 40】 In formula (2), R ｓ is a group represented by the said formula (2a), R ２１ and R ２２ are hydrogen atoms, a polymer.

10. The polymer according to claim 6, wherein the first structural unit derived from maleic anhydride further includes a structural unit represented by formula (MA), the structural unit represented by the said formula (MA) is 10 mol% or more and 30 mol% or less with respect to all the structural units of the polymer, 【Chemical formula 41】 In formula (MA), R ２１ and R ２２ are hydrogen atoms, a polymer.

11. The polymer according to claim 6, the said polymer has a structure represented by formula (P2), 【Chemical formula 42】 In formula (P2), n is an integer from 1 to 6, p and q represent the molar contents of the structural units A and B contained in each polymer chain within n [ ], p and q may be the same or different for each polymer chain within n [ ], p + q = 1, p is 0 or more, q is 0 or more, when the molar contents of the respective structural units A and B contained in the said polymer are p ｔ and q ｔ respectively, then p ｔ + q ｔ = 1, p ｔ is greater than 0, q ｔ is greater than 0, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound having 2 to 6 functional groups, A represents one second structural unit selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), the structural unit represented by the formula (IN), the structural unit represented by the formula (AK), and the structural unit represented by the formula (CA), B contains the first structural unit derived from maleic anhydride, A polymer in which a plurality of As and Bs may be the same or different.

12. The polymer according to claim 7, The polymer has a structure represented by the formula (P3), 【Chemical Formula 43】 In the formula (P3), n is an integer of 1 to 6, p, q, and r represent the molar contents of the structural units A, B, and C contained in each polymer chain within n [ ], p, q, and r may be the same or different for each polymer chain within n [ ], p + q + r = 1, p is 0 or more, q is 0 or more, and r is 0 or more, When the molar contents of the respective structural units A, B, and C contained in the polymer are p ｔ , q ｔ and r ｔ respectively, p ｔ + q ｔ + r ｔ = 1, p ｔ is greater than 0, q ｔ is greater than 0, r ｔ is greater than 0, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound having 2 to 6 functional groups, A represents one of the second structural units selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), the structural unit represented by the formula (IN), the structural unit represented by the formula (AK), and the structural unit represented by the formula (CA). B contains the first structural unit derived from maleic anhydride. C represents one of the third structural units selected from the structural unit represented by the formula (MI) and the structural unit represented by the formula (AD). A plurality of As, Bs, and Cs may be the same or different, and the polymer.

13. A polymer having a structure represented by the formula (P2), The softening point of the polymer measured under the following (Condition 1) is 0 °C or higher and 100 °C or lower. (Condition 1: 0.1 to 1.0 mg of the polymer is placed in an aluminum sample pan, and in a nitrogen atmosphere, using a differential thermal analyzer, the measurement mode is compression, the load is 30 mN, and in the range of 30 °C to 200 °C, the temperature is raised at a rate of 3 °C / min. The amount by which the polymer softens and deforms due to heating is detected as the displacement amount (μm), and the intersection of the extension of the straight line part without displacement on the low temperature side or the tangent line of the minimum part of the displacement speed and the tangent line of the maximum part of the displacement speed is taken as the softening point.) [Chemical formula 44] In the formula (P2), n is an integer from 1 to 6. p and q represent the molar contents of the structural units A and B contained in each polymer chain within n [ ]. p and q may be the same or different for each polymer chain within n [ ]. p + q = 1, p is 0 or more, and q is 0 or more. When the molar contents of the respective structural units A and B contained in the polymer are p ｔ and q ｔ respectively, p ｔ + q ｔ = 1, p ｔ is greater than 0, and q ｔ is greater than 0, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound having 2 to 6 functional groups, A represents one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), the structural unit represented by formula (IN), the structural unit represented by formula (AK), and the structural unit represented by formula (CA), B contains at least one structural unit derived from maleic anhydride selected from the structure represented by formula (1) and the structure represented by formula (2), A plurality of As and Bs may be the same or different from each other, When the structural unit A contains the structural unit represented by the formula (NB), the structural unit represented by the formula (NB) is 35 mol% or more and 60 mol% or less based on all the structural units of the polymer, When the structural unit A contains the structural unit represented by the formula (ST), the structural unit represented by the formula (ST) is 35 mol% or more and 60 mol% or less based on all the structural units of the polymer, When the structural unit A contains the structural unit represented by the formula (IN), the structural unit represented by the formula (IN) is 7 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the structural unit A contains the structural unit represented by the formula (AK), the structural unit represented by the formula (AK) is 5 mol% or more and 50 mol% or less based on all the structural units of the polymer, When the structural unit A contains the structural unit represented by the formula (CA), the structural unit represented by the formula (CA) is 5 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the structural unit B contains the structural unit represented by the formula (1), The structural unit represented by the formula (1) is 1 mol% or more and 18 mol% or less based on all the structural units of the polymer. When the structural unit B contains the structural unit represented by the formula (2), The structural unit represented by the formula (2) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer. [Chemical Formula 45] In the formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a １ is 0, 1 or 2. [Chemical Formula 46] In the formula (ST), R ４０ , R ４１ and R ４２ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４３ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [Chemical Formula 47] In the formula (IN), R ６１ to R ６８ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [Chemical Formula 48] In the formula (AK), at least one of R ７１ , R ７２ , R ７３ and R ７４ is a linear or branched alkyl group having 3 to 30 carbon atoms, and the rest of R ７１ , R ７２ , R ７３ and R ７４ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms. [Chemical Formula 49] In the formula (CA), X ５１ is a single bond or a linear or branched alkylene group having 1 to 30 carbon atoms. X ５１ is a single bond, R ５１ , R ５２ and R ５３ at least one of which is a linear or branched alkyl group having 2 to 30 carbon atoms, and the rest of R ５１ , R ５２ and R ５３ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, X ５１ is a linear or branched alkylene group having 1 to 30 carbon atoms, R ５１ , R ５２ and R ５３ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, [Chemical Formula 50] [Chemical Formula 51] In Formula (1) and Formula (2), R ２１ and R ２２ are hydrogen atoms, R ｐ is at least one selected from the group consisting of a group represented by Formula (1b), a group represented by Formula (1c), and a group represented by Formula (1d), R ｓ is a group represented by Formula (2a), [Chemical Formula 52] In Formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different, X １ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and a plurality of Xs １ may be the same or different, X １' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z' - (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X ２ is a group obtained by removing (k + 1) hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms, [Chemical formula 53] In formula (1c), k, R, X １ and X ２ are the same as R, k, X in formula (1b), respectively, １ and X ２ respectively, and a plurality of Rs may be the same as or different from each other, and a plurality of Xs １ may be the same as or different from each other, X ３ is a single bond or a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms, X ６ is an alkylene group having 1 to 6 carbon atoms, [Chemical formula 54] In formula (1d), n is an integer of 2 to 5, R is independently a hydrogen atom or a methyl group, [Chemical formula 55] In formula (2a), X １０ is an alkylene group having 1 to 6 carbon atoms, R is a hydrogen atom or a methyl group, a polymer (however, the structural unit represented by the formula (NB), the structural unit represented by the formula (AD), at least one structural unit selected from the structural unit represented by the formula (1) and the structural unit represented by the formula (2), and is a polymer containing [Chemical formula 58] In formula (AD), R １１ and R １２ each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms, and R １３ and R １４ is a hydrogen atom (excluding polymers).

14. A polymer having a structure represented by formula (P3), wherein the softening point of the polymer measured under the following (Condition 1) is 0°C or higher and 100°C or lower, (Condition 1: 0.1 to 1.0 mg of the polymer is placed in an aluminum sample pan, and under a nitrogen atmosphere, using a differential thermal analyzer, the measurement mode is compression, the load is 30 mN, and the temperature is raised from 30°C to 200°C at a rate of 3°C / min. The amount by which the polymer softens and deforms upon heating is detected as the displacement amount (μm), and the intersection of the extension of the straight line portion without displacement on the low-temperature side or the tangent line of the minimum portion of the displacement rate and the tangent line of the maximum portion of the displacement rate is defined as the softening point). 【Chemical Formula 59】 In formula (P3), n is an integer from 1 to 6, p, q, and r represent the molar contents of structural units A, B, and C contained in each polymer chain within n [ ], p, q, and r may be the same or different for each polymer chain within n [ ], p + q + r = 1, p is 0 or more, q is 0 or more, and r is 0 or more, When the molar contents of each structural unit A, B, and C contained in the polymer are p ｔ , q ｔ and r ｔ respectively, then p ｔ + q ｔ + r ｔ = 1, p ｔ is greater than 0, q ｔ is greater than 0, and r ｔ is greater than 0, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a thiol group-containing compound having a monofunctional or bifunctional or higher up to hexafunctional group, A represents one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), the structural unit represented by formula (IN), the structural unit represented by formula (AK), and the structural unit represented by formula (CA), B contains at least one structural unit derived from maleic anhydride selected from the structure represented by formula (1) and the structure represented by formula (2), C represents one structural unit selected from the structural unit represented by formula (MI) and the structural unit represented by formula (AD), A plurality of As, Bs, and Cs may be the same or different from each other, When the structural unit A contains the structural unit represented by the formula (NB), The structural unit represented by the formula (NB) is 35 mol% or more and 60 mol% or less based on all the structural units of the polymer, When the structural unit A contains the structural unit represented by the formula (ST), The structural unit represented by the formula (ST) is 35 mol% or more and 60 mol% or less based on all the structural units of the polymer, When the structural unit A contains the structural unit represented by the formula (IN), The structural unit represented by the formula (IN) is 7 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the structural unit A contains the structural unit represented by the formula (AK), The structural unit represented by the formula (AK) is 5 mol% or more and 50 mol% or less based on all the structural units of the polymer, When the structural unit A contains the structural unit represented by the formula (CA), The structural unit represented by the formula (CA) is 5 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the structural unit B contains the structural unit represented by the formula (1), The structural unit represented by the formula (1) is 1 mol% or more and 18 mol% or less based on all the structural units of the polymer. When the structural unit B contains the structural unit represented by the formula (2), The structural unit represented by the formula (2) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer. When the structural unit C contains the structural unit represented by the formula (MI), The structural unit represented by the formula (MI) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer. When the structural unit C contains the structural unit represented by the formula (AD), The structural unit represented by the formula (AD) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer. [Chemical Formula 60] In the formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a １ is 0, 1 or 2. [Chemical Formula 61] In the formula (ST), R ４０ , R ４１ and R ４２ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４３ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [Chemical Formula 62] In the formula (IN), R ６１ to R ６８ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [Chemical Formula 63] In the formula (AK), at least one of R ７１ , R ７２ , R ７３ and R ７４ is a linear or branched alkyl group having 3 to 30 carbon atoms, and R ７１ , R ７２ , R ７３ and R ７４ and the rest of R are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, [Chemical Formula 64] In formula (CA), X ５１ is a single bond or a linear or branched alkylene group having 1 to 30 carbon atoms, X ５１ When X is a single bond, at least one of R ５１ , R ５２ and R ５３ is a linear or branched alkyl group having 2 to 30 carbon atoms, and the rest of R ５１ , R ５２ and R ５３ are a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, X ５１ When X is a linear or branched alkylene group having 1 to 30 carbon atoms, R ５１ , R ５２ and R ５３ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, [Chemical Formula 65] [Chemical Formula 66] In formulas (1) and (2), R ２１ and R ２２ are hydrogen atoms, R ｐ is at least one selected from the group represented by formula (1b), the group represented by formula (1c), and the group represented by formula (1d), R ｓ is the group represented by formula (2a), [Chemical Formula 67] In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different, X １ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms). When there are a plurality of Xs, １ they may be the same or different, X １ ’ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X’-Z’- (X’ is an alkylene group having 1 to 6 carbon atoms, and Z’ is -O- or -COO-), X ２ is a group obtained by removing (k + 1) hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms, 【Chemical Formula 68】 In formula (1c), k, R, X １ and X ２ are the same as R, k, X, １ and X ２ in formula (1b), respectively. A plurality of Rs may be the same or different from each other, and a plurality of Xs １ may be the same or different from each other, X ３ is a single bond or a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms, X ６ is an alkylene group having 1 to 6 carbon atoms, 【Chemical Formula 69】 In formula (1d), n is an integer from 2 to 5, R is independently a hydrogen atom or a methyl group, 【Chemical Formula 70】 In formula (2a), X １０ is an alkylene group having 1 to 6 carbon atoms, and R is a hydrogen atom or a methyl group, 【Chemical Formula 71】 In formula (MI), R ３１ is a hydrogen atom or an organic group having 1 to 30 carbon atoms, R ３２ and R ３３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, 【Chemical Formula 72】 In formula (AD), R １１ and R １２ are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, R １３ and R １４ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a polymer (however, the structural unit represented by the said formula (NB), the structural unit represented by the said formula (AD), at least one structural unit selected from the structural unit represented by the said formula (1) and the structural unit represented by the said formula (2), a polymer containing) excluding.)

15. The polymer according to claim 13, wherein the structural unit B further includes at least one structural unit selected from the structural unit represented by formula (8), the structural unit represented by formula (9), the structural unit represented by formula (5), and the structural unit represented by formula (6), when the structural unit B includes the structural unit represented by the said formula (8), the structural unit represented by the said formula (8) is 0.5 mol% or more and 12 mol% or less with respect to all the structural units of the polymer, when the structural unit B includes the structural unit represented by the said formula (9), the structural unit represented by the said formula (9) is 0.5 mol% or more and 12 mol% or less with respect to all the structural units of the polymer, when the structural unit B includes the structural unit represented by the said formula (5), the structural unit represented by the said formula (5) is 1 mol% or more and 9 mol% or less with respect to all the structural units of the polymer, when the structural unit B includes the structural unit represented by the said formula (6), The structural unit represented by the formula (6) is 1 mol% or more and 8 mol% or less based on all the structural units of the polymer, [Chemical formula 73] [Chemical formula 74] In formula (8) and formula (9), Z is a (meth)acryloyl group, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, R ２１ and R ２２ are hydrogen atoms, R ｐ is at least one selected from the group represented by the formula (1b), the group represented by the formula (1c), and the group represented by the formula (1d), R ｓ is the group represented by the formula (2a), [Chemical formula 75] [Chemical formula 76] In formula (5) and formula (6), Z is a (meth)acryloyl group, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, R ２１ and R ２２ are hydrogen atoms, a polymer.

16. The polymer according to claim 14, The structural unit B further includes at least one structural unit selected from the structural unit represented by formula (8), the structural unit represented by formula (9), the structural unit represented by formula (5), and the structural unit represented by formula (6), When the structural unit B contains the structural unit represented by the formula (8), The structural unit represented by the formula (8) is 0.5 mol% or more and 12 mol% or less based on all the structural units of the polymer, When the structural unit B contains the structural unit represented by the formula (9), the structural unit represented by the formula (9) is 0.5 mol% or more and 12 mol% or less based on all the structural units of the polymer, When the structural unit B contains the structural unit represented by the formula (5), the structural unit represented by the formula (5) is 1 mol% or more and 9 mol% or less based on all the structural units of the polymer, When the structural unit B contains the structural unit represented by the formula (6), the structural unit represented by the formula (6) is 1 mol% or more and 8 mol% or less based on all the structural units of the polymer, 【Chemical Formula 77】 【Chemical Formula 78】 In the formula (8) and the formula (9), Z is a (meth)acryloyl group, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, R ２１ and R ２２ are hydrogen atoms, R ｐ is at least one selected from the group consisting of the group represented by the formula (1b), the group represented by the formula (1c), and the group represented by the formula (1d), R ｓ is the group represented by the formula (2a), 【Chemical Formula 79】 【Chemical Formula 80】 In the formula (5) and the formula (6), Z is a (meth)acryloyl group, Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, R ２１ and R ２２ are hydrogen atoms, a polymer.

17. The polymer according to claim 13, wherein the structural unit B further includes a structural unit represented by the formula (MA), and the structural unit represented by the formula (MA) is 10 mol% or more and 30 mol% or less based on all the structural units of the polymer, 【Chemical formula 81】 In the formula (MA), R ２１ and R ２２ are hydrogen atoms, the polymer.

18. A polymer having a structure represented by the formula (P3), wherein the softening point of the polymer measured under the following (Condition 1) is 0 °C or higher and 100 °C or lower, (Condition 1: 0.1 to 1.0 mg of the polymer is placed in an aluminum sample pan, and under a nitrogen atmosphere, using a differential thermal analyzer, the measurement mode is compression, the load is 30 mN, and the temperature is raised at a rate of 3 °C / min in the range from 30 °C to 200 °C. The amount by which the polymer softens and deforms upon heating is detected as the displacement amount (μm), and the intersection of the extension of the straight line portion without displacement on the low temperature side or the tangent line of the minimum portion of the displacement rate and the tangent line of the maximum portion of the displacement rate is defined as the softening point) 【Chemical formula 59】 In the formula (P3), n is an integer from 1 to 6, p, q, and r represent the molar contents of the structural units A, B, and C contained in each polymer chain within n [ ], p, q, and r may be the same or different for each polymer chain within n [ ], p + q + r = 1, p is 0 or more, q is 0 or more, and r is 0 or more, When the molar contents of the respective structural units A, B, and C contained in the polymer are p ｔ , q ｔ and r ｔ respectively, then p ｔ + q ｔ + r ｔ = 1, p ｔ is greater than 0, q ｔis greater than 0, r ｔ is greater than 0, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound having 2 to 6 functional groups, A represents one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), the structural unit represented by formula (IN), the structural unit represented by formula (AK), and the structural unit represented by formula (CA), B includes at least one structural unit derived from maleic anhydride selected from the structure represented by formula (1) and the structure represented by formula (2), and at least one structural unit selected from the structural unit represented by formula (8), the structural unit represented by formula (9), the structural unit represented by formula (5), and the structural unit represented by formula (6), C represents one structural unit selected from the structural unit represented by formula (MI) and the structural unit represented by formula (AD), Plural A's, B's, and C's may be the same or different from each other, When the structural unit A includes the structural unit represented by the formula (NB), the structural unit represented by the formula (NB) is 35 mol% or more and 60 mol% or less based on all the structural units of the polymer, When the structural unit A includes the structural unit represented by the formula (ST), the structural unit represented by the formula (ST) is 35 mol% or more and 60 mol% or less based on all the structural units of the polymer, When the structural unit A includes the structural unit represented by the formula (IN), the structural unit represented by the formula (IN) is 7 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the structural unit A includes the structural unit represented by the formula (AK), the structural unit represented by the formula (AK) is 5 mol% or more and 50 mol% or less based on all the structural units of the polymer, When the structural unit A includes the structural unit represented by the formula (CA), The structural unit represented by the formula (CA) is 5 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the structural unit B includes the structural unit represented by the formula (1), The structural unit represented by the formula (1) is 1 mol% or more and 18 mol% or less based on all the structural units of the polymer, When the structural unit B includes the structural unit represented by the formula (2), The structural unit represented by the formula (2) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the structural unit B includes the structural unit represented by the formula (8), The structural unit represented by the formula (8) is 0.5 mol% or more and 12 mol% or less based on all the structural units of the polymer, When the structural unit B includes the structural unit represented by the formula (9), The structural unit represented by the formula (9) is 0.5 mol% or more and 12 mol% or less based on all the structural units of the polymer, When the structural unit B includes the structural unit represented by the formula (5), The structural unit represented by the formula (5) is 1 mol% or more and 9 mol% or less based on all the structural units of the polymer, When the structural unit B includes the structural unit represented by the formula (6), The structural unit represented by the formula (6) is 1 mol% or more and 8 mol% or less based on all the structural units of the polymer, When the structural unit C includes the structural unit represented by the formula (MI), The structural unit represented by the formula (MI) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer, When the structural unit C includes the structural unit represented by the formula (AD), The structural unit represented by the formula (AD) is 2 mol% or more and 25 mol% or less based on all the structural units of the polymer, [Chemical Formula 60] In formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a １ is 0, 1, or 2, [Chemical Formula 61] In formula (ST), R ４０ , R ４１ and R ４２ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４３ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, [Chemical Formula 62] In formula (IN), R ６１ to R ６８ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, [Chemical Formula 63] In formula (AK), at least one of R ７１ , R ７２ , R ７３ and R ７４ is a linear or branched alkyl group having 3 to 30 carbon atoms, and the remainder of R ７１ , R ７２ , R ７３ and R ７４ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, [Chemical Formula 64] In formula (CA), X ５１ is a single bond or a linear or branched alkylene group having 1 to 30 carbon atoms, When X ５１ is a single bond, at least one of R ５１ , R ５２ and R ５３ is a linear or branched alkyl group having 2 to 30 carbon atoms, and R ５１ , R ５２ and R ５３The remainder is a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, X ５１ When ５１ is a linear or branched alkylene group having 1 to 30 carbon atoms, R ５１ , R ５２ and R ５３ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms, [Chemical Formula 65] [Chemical Formula 66] In Formula (1) and Formula (2), R ２１ and R ２２ are hydrogen atoms, R ｐ is at least one selected from the group represented by Formula (1b), the group represented by Formula (1c), and the group represented by Formula (1d), R ｓ is the group represented by Formula (2a), [Chemical Formula 67] In Formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different, X １ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and a plurality of Xs １ may be the same or different, X １ ’ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X’-Z’- (X’ is an alkylene group having 1 to 6 carbon atoms, and Z’ is -O- or -COO-), X ２ is a group obtained by removing (k + 1) hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms, [Chemical Formula 68] In Formula (1c), k, R, X １and X ２ are, respectively, R, k, X in formula (1b) １ and X ２ are synonymous with, and the plurality of Rs may be the same as or different from each other, and the plurality of Xs １ may be the same as or different from each other, X ３ is a single bond or a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms, X ６ is an alkylene group having 1 to 6 carbon atoms, [Chemical Formula 69] In formula (1d), n is an integer of 2 to 5, R is independently a hydrogen atom or a methyl group, [Chemical Formula 70] In formula (2a), X １０ is an alkylene group having 1 to 6 carbon atoms, R is a hydrogen atom or a methyl group, [Chemical Formula 77] [Chemical Formula 78] In formulas (8) and (9), Z is a (meth)acryloyl group, Q is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, R ２１ and R ２２ are hydrogen atoms, R ｐ is at least one selected from the group represented by the formula (1b), the group represented by the formula (1c), and the group represented by the formula (1d), R ｓ is the group represented by the formula (2a), [Chemical Formula 79] [Chemical Formula 80] In formulas (5) and (6), Z is a (meth)acryloyl group, Q is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, X represents an oxygen atom, R ２１ and R ２２ are hydrogen atoms, 【Chemical Formula 71】 In formula (MI), R ３１ is a hydrogen atom or an organic group having 1 to 30 carbon atoms, R ３２ and R ３３ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, 【Chemical Formula 72】 In formula (AD), R １１ and R １２ are each independently a linear or branched alkyl group having 1 to 12 carbon atoms, R １３ and R １４ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Polymer.

19. The polymer according to any one of Claims 1, 6, 13, 14, and 18, wherein the weight average molecular weight of the polymer is 2,000 or more and 50,000 or less.

20. The polymer according to any one of Claims 1, 6, 13, 14, and 18, wherein the melting point of the polymer is 20°C or more and 130°C or less.

21. A polymer solution containing the polymer according to any one of Claims 1, 6, 13, 14, and 18.

22. The polymer solution according to Claim 21, A polymer solution further containing a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

23. The polymer solution according to claim 21, A polymer solution used for forming a color filter, a black matrix, a spacer, or a partition wall material.

24. The polymer according to any one of claims 1, 6, 13, 14, 18, and a photo radical polymerization initiator, a photosensitive resin composition.

25. A cured product formed from the photosensitive resin composition according to claim 24.

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