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

Abstract

To provide a polymer which a resin cured product has improved heat characteristics, thereby is excellent in workability and pattern formability in photolithography processing, and is excellent in resin cured product sensitivity having a good balance among sensitivity, alkali solubility and heat-yellowing resistance.SOLUTION: A polymer includes at least one structural unit selected from a structural unit derived from carboxylic acid-containing alkene, a structural unit including two or more (meth)acryloyl groups, and a structural unit including one (meth)acryloyl group.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 technology]

[0002] A liquid crystal display device or a solid-state imaging device is usually provided with a color filter, a black matrix, a spacer (e.g., a photospacer, a colored spacer, a black spacer), and a partition material (e.g., a transparent bank, a black bank). The color filter, the black matrix, the spacer, and the partition material are configured such that structures such as a colored pattern and a protective film are formed on a substrate. As a method for forming the colored pattern and the protective film among these structures, a method of forming them by photolithography using a photosensitive resin composition is mainstream. Regarding the photosensitive resin composition, various studies have been made in the past, and for example, Patent Document 1 describes a photosensitive resin composition containing an alkali-soluble resin having at least a group having an acidic group and two or more different polymerizable unsaturated groups in at least a side chain, a polymerizable compound, and a photopolymerization initiator. In addition, an example of Patent Document 1 describes that a methacrylic acid / allyl methacrylate / 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] International Publication No. 2012 / 147706 Summary of the Invention [Problem to be solved by the invention]

[0004] A photosensitive resin composition for forming a color filter, a black matrix, a spacer, or a partition material uses a resin having a property of being cured by polymerization reaction caused by light. A color filter, a black matrix, a spacer, or a partition material is produced by patterning a photosensitive resin composition by exposure and development, and then curing the same. Although "high sensitivity" seems to be a general issue for a photosensitive resin composition, a higher level of high sensitivity is required with the increasing complexity and popularity of display devices and imaging devices. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, and the higher the productivity. In addition, the photosensitive resin composition is required to have excellent processability in a development process using an alkaline developer. Furthermore, the cured product of the photosensitive resin composition is required to have high transparency. [Means for solving the problem]

[0005] The present inventors have found that by improving the polymer used in the photosensitive resin composition and the formulation of the composition, it is possible to obtain a cured resin product which has good sensitivity, high alkali solubility, and reduced yellowing, and have arrived at the present invention.

[0006] According to the present invention, there are provided the following polymer, a polymer solution or a photosensitive resin composition containing the polymer, and a cured product of the photosensitive resin composition. [1] A structural unit represented by the formula (CA); and A polymer comprising at least one structural unit selected from a structural unit represented by formula (1-2) and a structural unit represented by formula (1-3), [ka] In formula (CA), X 51 is a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, X 51 is a single bond, R 51 , R 52 and R 53At least one of R is a linear or branched alkyl group having 2 to 20 carbon atoms; 51 , R 52 and R 53 the remainder being a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms; X 51 is a linear or branched alkyl group having 1 to 20 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 20 carbon atoms, [ka] In formula (1-2), R p is a group having two or more (meth)acryloyl groups, R 22 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, [ka] 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. [2] The polymer according to item [1], The polymer further comprises at least one selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI), [ka] In formula (NB), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms; a1 represents 0, 1, or 2; [ka] In formula (ST), R 40 , R41 and R 42 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, R 43 each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, [ka] In formula (MI), 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; polymer. [3] The polymer according to item [1] or [2], further comprising a structural unit represented by formula (1-1), [ka] In formula (1-1), 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, a single bond, 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 be condensed to form a cyclic group; R 21 is a hydrogen atom or an organic group having 1 to 3 carbon atoms. [4] The polymer according to any one of items [1] to [3], further comprising a structural unit represented by formula (1-4): [ka] In formula (1-4), R 22 is a hydrogen atom or an organic group having 1 to 3 carbon atoms. [5] The polymer according to any one of items [1] to [4], further comprising at least one selected from the structural unit represented by formula (1) and the structural unit represented by formula (2), [ka] [ka] In formula (1) and formula (2), R p is a group having two or more (meth)acryloyl groups, R s is a group having one (meth)acryloyl group, R 21 and R 22 each independently represents a hydrogen atom or an organic group having 1 to 3 carbon atoms. [6] The polymer according to any one of items [1] to [5], further comprising a structural unit represented by formula (3): [ka] In formula (3), R 21 and R 22 each independently represents a hydrogen atom or an organic group having 1 to 3 carbon atoms. [7] The polymer according to any one of items [1] to [6], further comprising at least one selected from a structural unit represented by formula (8) and a structural unit represented by formula (9), [ka] [ka] In formula (8) and formula (9), R p is a group having two or more (meth)acryloyl groups, R 22 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R s is a group having one (meth)acryloyl group, R 21 and R 22 each independently represents 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, a single bond, 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 be condensed to form a cyclic group. [8] The polymer according to any one of items [1] to [7], further comprising a structural unit represented by formula (5): [ka] In formula (5), 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, a single bond, 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 be condensed to form a cyclic group; R 21 and R 22 each independently represents a hydrogen atom or an organic group having 1 to 3 carbon atoms. [9] The polymer according to any one of items [1] to [8], further comprising a structural unit represented by formula (6): [ka] In formula (6), 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, a single bond, 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 be condensed to form a cyclic group; R 21 and R 22 each independently represents a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[10] The polymer according to claim 1, further comprising a structural unit represented by formula (MA): [ka] In formula (MA), R 21 and R 22 each independently represents a hydrogen atom or an organic group having 1 to 3 carbon atoms.

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

[10] , The polymer includes a structure represented by the formula (1-2), R in the above formula (1-2) p is at least one selected from a group represented by formula (1b), a group represented by formula (1c), and a group represented by formula (1d), [ka] In formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R 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 -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X 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, [ka] In formula (1c), k, R, X 1 and X 2 are R, k, and X in formula (1b), respectively. 1 and X 2and R may be the same or different from each other, and X 1 may be the same or different, X 3 is a single bond or a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 each independently represents 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, [ka] In formula (1d), n is an integer from 2 to 5, R is independently a hydrogen atom or a methyl group.

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

[11] , The polymer contains a structural unit represented by formula (1-3), R in the above formula (1-3) s is a group represented by formula (2a), [ka] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. polymer.

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

[12] , The polymer has a structure represented by formula (P2): [ka] 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 of the n polymer chains in the brackets [ ]; p and q may be the same or different for each of the n polymer chains in the brackets [ ]; p+q=1, p is greater than or equal to 0, and q is greater than or equal to 0; The molar contents of the structural units A and B contained in the polymer are respectively represented by p t and q t Then, p t +q t = 1, and 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 di- or higher-functional thiol group-containing compound, A represents a structural unit represented by formula (CA), B includes at least one structural unit selected from the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), A polymer in which a plurality of A's and a plurality of B's ​​may be the same or different.

[14] The polymer according to any one of items [2] to

[13] , The polymer has a structure represented by formula (P3): [ka] 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 in each of the n polymer chains in the brackets [ ]; p, q, and r may be the same or different for each of the n polymer chains in the [ ]; p+q+r=1, where p is greater than or equal to 0, q is greater than or equal to 0, and r is greater than or equal to 0; The molar contents of the structural units A, B, and C contained in the polymer are respectively represented by p t , q t , and r t Then, p t +q t +r t = 1, and p t is greater than 0, and 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 monofunctional or di- or higher-functional thiol group-containing compound, A represents a structural unit represented by formula (CA), B includes 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 includes at least one selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), and the structural unit represented by the formula (MI), A polymer in which a plurality of A's, B's, and C's may be the same or different.

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

[14] , The weight average molecular weight of the polymer is 3,000 or more and 50,000 or less.

[16] A polymer solution comprising the polymer according to any one of items [1] to

[15] .

[17] The polymer solution according to item

[16] , The polymer solution further comprises a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

[18] The polymer solution according to item

[16] or

[17] , A polymer solution used to form color filters, black matrices, spacers, or partition materials.

[19] A polymer according to any one of items [1] to

[15] , A photoradical polymerization initiator, Photosensitive resin composition.

[20] A cured product formed from the photosensitive resin composition according to item

[19] .

[21] A structural unit represented by the formula (CA); and A structural unit represented by the formula (MA); A polymer comprising: [ka] In formula (CA), X 51 is a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, X 51 is a single bond, R 51 , R 52 and R 53 At least one of R is a linear or branched alkyl group having 2 to 20 carbon atoms; 51 , R 52 and R 53 the remainder being a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms; X 51 is a linear or branched alkyl group having 1 to 20 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 20 carbon atoms, [ka] In formula (MA), R 21 and R 22 each independently represents a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[22] The polymer according to item

[21] , The polymer further comprises at least one selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI), [ka] In formula (NB), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms; a1 represents 0, 1, or 2; [ka] In formula (ST), R 40 , R 41 and R 42are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, R 43 each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, [ka] In formula (MI), 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; polymer.

[23] The polymer according to item

[21] or

[22] , The polymer has a structure represented by formula (P2'): [ka] 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 of the n polymer chains in the brackets [ ]; p and q' may be the same or different for each of the n polymer chains in the brackets [ ]; p+q'=1, p is greater than or equal to 0, and q' is greater than or equal to 0; The molar contents of the structural units A and B' contained in the polymer are respectively represented by p t and q t ', then p t +q t '=1, and 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 di- or higher-functional thiol group-containing compound, A represents a structural unit represented by formula (CA), B' represents a structural unit represented by formula (MA), A polymer in which a plurality of A's and a plurality of B's ​​may be the same or different.

[24] The polymer according to item

[22] or

[23] , The polymer has a structure represented by formula (P3'): [ka] 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 in each of the n polymer chains in the brackets [ ]; p, q', and r may be the same or different for each of the n polymer chains in the [ ]; p+q'+r=1, where p is greater than or equal to 0, q' is greater than or equal to 0, and r is greater than or equal to 0; The molar contents of the structural units A, B', and C contained in the polymer are respectively represented by p t , q t ', and r t Then, p t +q t '+r t = 1, and p t is greater than 0, and 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 monofunctional or di- or higher-functional thiol group-containing compound, A represents a structural unit represented by formula (CA), B' represents a structural unit represented by formula (MA), C includes at least one selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), and the structural unit represented by the formula (MI), A polymer in which a plurality of A's, a plurality of B's, and a plurality of C's may be the same or different.

[25] The polymer according to any one of items

[21] to

[24] , The weight average molecular weight of the polymer is 2,000 or more and 30,000 or less.

[0007] According to the present invention, there is provided a polymer as a resin material for use in a photosensitive resin composition which has good sensitivity and high alkali solubility, and therefore excellent developability, and which also exhibits reduced yellowing and therefore high resistance to thermal discoloration. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram (cross-sectional view) illustrating a schematic example of the structure of a liquid crystal display device and / or a solid-state imaging device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, an embodiment of the present invention will be described. In all drawings, similar components are given similar symbols and their explanations are omitted as appropriate. In addition, all drawings are for explanatory purposes only. The shapes and dimensional ratios of each member in the drawings do not necessarily correspond to actual objects. In this specification, the expression "a to b" in the explanation of a numerical range means "a or more and b or less" unless otherwise specified. For example, "5 to 90%" means "5% or more and 90% or less".

[0010] In the description of groups (atomic groups) in this specification, when a description is made without specifying whether the group is substituted or unsubstituted, the description includes both groups having no substituents and groups having a substituent. For example, the term "alkyl group" includes not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having a substituent (substituted alkyl groups).

[0011] In this specification, the term "(meth)acrylic" refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In particular, the term "(meth)acryloyl group" in this specification represents a concept that encompasses 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, structural units or compounds represented by the same structural formula have the same definitions throughout all embodiments, and preferred embodiments are also the same.

[0013] [First embodiment] (Polymer P(I)) The polymer in the first embodiment of the present invention (hereinafter referred to as "polymer P(I)") contains a structural unit represented by formula (CA) and at least one structural unit selected from a structural unit represented by formula (1-2) and a structural unit represented by formula (1-3).

[0014] [ka]

[0015] In formula (CA), X 51 is a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, X 51 is a single bond, R 51 , R 52 and R 53 At least one of R is a linear or branched alkyl group having 2 to 20 carbon atoms; 51 , R 52 and R 53 the remainder being a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms; X 51 is a linear or branched alkyl group having 1 to 20 carbon atoms, R 51 , R 52 and R 53are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms.

[0016] [ka]

[0017] In formula (1-2), R p is a group having two or more (meth)acryloyl groups, R 22 is a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0018] [ka]

[0019] 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.

[0020] The polymer P(I) of this embodiment also has a structural unit derived from a carboxylic acid-containing alkene represented by formula (CA). By introducing the structural unit (CA) derived from a carboxylic acid-containing alkene into the polymer P(I), the alkali solubility of the polymer P(I) can be improved without causing any change in sensitivity or heat yellowing resistance. Therefore, the photosensitive resin composition containing the polymer P(I) can be suitably used for producing a film or filter for use in a liquid crystal display device or a solid-state imaging device that requires heat resistance.

[0021] The polymer P(I) of this 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). This allows the photosensitive resin composition containing the polymer P(I) to have excellent sensitivity when subjected to photolithography processing. This is believed to be 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).

[0022] In the structural unit represented by formula (CA), X 51 is a single bond or a linear or branched alkylene group having one or more carbon atoms, X 51 is a single bond, R 51 , R 52 and R 53 At least one of R is a linear or branched alkyl group having 2 or more carbon atoms; 51 , R 52 and R 53 the remainder being a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms; X 51 is a linear or branched alkyl group having one 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.

[0023] In a preferred embodiment, in the structural unit represented by formula (CA), X 51 is a linear or branched alkylene group having one 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. In another preferred embodiment, X 51 is a linear or branched alkylene group having one or more carbon atoms, R51 , R 52 and R 53 is a hydrogen atom. X 51 In the embodiment where X is a linear or branched alkylene group having one or more carbon atoms, 51 is more preferably a linear alkylene group having 1 or more carbon atoms, even 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. 11 The upper limit of the number of carbon atoms in the linear or branched alkylene group having 1 or more carbon atoms constituting the above formula is, for example, 30 or less carbon atoms, preferably 25 or less carbon atoms, and more preferably 20 or less carbon atoms.

[0024] In yet another embodiment, in the structural unit represented by formula (CA), X 51 is a single bond, and R 51 , R 52 and R 53 At least one of R is a linear or branched alkyl group having 2 or more carbon atoms; 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. More preferably, X 51 is a single bond, and R 51 is a linear or branched alkyl group having two or more carbon atoms, R 52 and R 53 is a hydrogen atom.

[0025] Among these, the structural unit represented by formula (CA) is easily introduced into the polymer P(I), which facilitates molecular design, and the resulting polymer P(I) has excellent alkali solubility without impairing heat yellowing resistance. Therefore, in the structural unit represented by formula (CA), X 51 is a linear or branched alkylene group having one or more carbon atoms, R 51 , R 52 and R 53 is preferably a hydrogen atom. 51The greater the number of carbon atoms in the alkylene group constituting the formula (CA), the lower the softening point and melting point of the resulting polymer P(I). Therefore, the number of carbon atoms in the structural unit of formula (CA) can be selected depending on the softening point or melting point desired in the application of the polymer P(I).

[0026] The proportion of the structural unit represented by formula (CA) in all structural units constituting the polymer P(I) is preferably 2 to 30 mol%, more preferably 3 to 28 mol%, and further preferably 5 to 25 mol%. By setting the proportion of the structural unit represented by formula (CA) in the polymer P(I) within the above range, it is possible to obtain a polymer P(I) having a low softening point and a low melting point, and also having a highly improved balance of sensitivity, alkali solubility, and heat discoloration resistance.

[0027] The polymer P(I) contains a structural unit having two or more (meth)acryloyl groups (-C(=O)-CH=CH2) represented by formula (1-2), or a structural unit having one (meth)acryloyl group represented by formula (1-3), or a combination thereof. By containing such a structural unit, the polymer P(I) has better sensitivity in exposure processing.

[0028] 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. 21 and R 22 and R are preferably both hydrogen atoms.

[0029] In the structural unit represented by formula (1-2), R p R 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. pBy optimizing the number of (meth)acryloyl groups contained in, the sensitivity of the polymer P(I) containing the same can be further increased in exposure treatment. In addition, it becomes easier to achieve a high degree of compatibility between the sensitivity and alkali solubility of the polymer P(I). Furthermore, the heat resistance of the polymer P(I) can be improved.

[0030] R in formula (1-2) p is preferably a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d), and includes at least one selected from these. By being such a group, it tends to be easy to obtain the various effects described above.

[0031] [ka]

[0032] In formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R 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 -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X 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 in view of further improving sensitivity (ease of polymerization) and the like. Although k may be 2 or 3, it is preferably 3 from the viewpoints of availability of raw materials and further improvement of sensitivity.

[0033] X 1When is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 When X is an alkylene group having 1 to 6 carbon atoms, 1 is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH2- (methylene group).

[0034] X 1 When is a group represented by -ZX- (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 further preferably -CH2-CH2- (ethylene group) or -CH2-CH(CH3)-.

[0035] X 1 When X′ is an alkylene group having 1 to 6 carbon atoms, specific embodiments thereof are 1 is the same as: X 1 When X′ is a group represented by —X′-Z′-, specific embodiments of X′ are the same as those of X described above.

[0036] X 2 The (k+1)-valent organic group having 1 to 12 carbon atoms may be any group obtained by removing (k+1) hydrogen atoms from any organic compound. The "any organic compound" here 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 is, for example, a group in which (k+1) hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group in which (k+1) hydrogen atoms have been removed from a linear hydrocarbon having 1 to 3 carbon atoms. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxyl group). In addition, 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 (for example, an isocyanuric acid structure).

[0037] [ka]

[0038] In formula (1c), k, R, X 1 and X 2 are R, k, and X in formula (1b), respectively. 1 and X 2 and R may be the same or different from each other, and X 1 may be the same or different, X 3 is a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 each independently represents 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.

[0039] R, k, X 1 and X 2 Specific embodiments, preferred embodiments, etc. of are the same as those explained for formula (1b). X 3 and X 6 Examples of the divalent organic group having 1 to 6 carbon atoms include a group in which two hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 6 carbon atoms. The hydrocarbon may contain an oxygen atom (for example, an ether bond or a hydroxyl group). The hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5The divalent organic group having 1 to 6 carbon atoms may be a linear or branched alkylene group. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

[0040] [ka]

[0041] In formula (1d), n is an integer of 2 to 5, and preferably 2 or 3. Specific embodiments and preferred embodiments of R are the same as those explained in formula (1b).

[0042] When the polymer P(I) contains a structural unit represented by formula (1-2), the proportion of the structural unit represented by formula (1-2) in all structural units of the polymer P(I) is preferably 3 to 40 mol %, more preferably 3 to 30 mol %.

[0043] In the structural unit represented by formula (1-3) which 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 the curability is increased in order to increase the sensitivity, the curing tends to proceed too much and the developability tends to deteriorate, while when the developability is improved, the curing tends to be insufficient. Therefore, it is preferable that the polymer P(I) contains either or both of the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), thereby achieving a good balance between the sensitivity and the developability.

[0044] R S is, for example, a group represented by the following formula (2a).

[0045] [ka]

[0046] In formula (2a), X 10is a divalent organic group, and R is a hydrogen atom or a methyl group. X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. X 10 As the divalent organic group, for example, an alkylene group is preferable. A part of -CH2- in this alkylene group may be an ether group (-O-). The alkylene group may be linear or branched, but is more preferably linear.

[0047] X 10 The divalent organic group X is more preferably a linear alkylene group having a total of 3 to 6 carbon atoms. 10 The number of carbon atoms (X 10 By appropriately selecting the chain length of the structural unit represented by formula (2), the structural unit represented by formula (2) can be more easily involved in the crosslinking reaction, thereby increasing the sensitivity.

[0048] X 10 The divalent organic group (for example, an alkylene group) may be substituted with any substituent, such as an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Also, X 10 The divalent organic group may be any group other than an alkylene group, for example, 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, and the like.

[0049] When the polymer P(I) contains a structural unit represented by formula (1-3), the proportion of the structural unit represented by formula (2) in all structural units of the polymer P(I) is preferably 5 to 30 mol %, more preferably 10 to 20 mol %.

[0050] When the polymer P(I) contains both the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), the total proportion of the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3) in the polymer P(I) is preferably 5 to 40 mol %, more preferably 10 to 35 mol %, and even more preferably 15 to 30 mol %, based on all the structural units constituting the polymer P(I).

[0051] In the structural unit represented by the above formula (MI) constituting the polymer P(I), R 32 and R 33 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. 32 and R 33 is preferably a hydrogen atom.

[0052] The polymer P(I) of this embodiment may contain, in addition to the above structural units, at least one selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI).

[0053] [ka]

[0054] In formula (NB), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms; a1 is 0, 1 or 2.

[0055] [ka]

[0056] 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, R 43are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms.

[0057] [ka]

[0058] In formula (MI), 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.

[0059] In the structural unit represented by the above formula (NB) which can constitute the polymer P(I), R 1 ~R 4 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above group include substituted or unsubstituted, linear or branched alkyl groups having 1 to 30 carbon atoms, and more specific examples thereof include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxy groups.

[0060] 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.

[0061] Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, 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.

[0062] 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. 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, a sec-butoxy group, an isobutoxy group, a tert-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.

[0063] In the structural unit represented by the formula (NB), R 1 , R 2 , R 3 and R 4 is preferably hydrogen or an alkyl group, and more preferably hydrogen. In addition, R 1 , R 2 , R 3 and R 4 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, R 1 , R 2 , R 3 and R 4 As the organic group having 1 to 30 carbon atoms, a fluorinated alkyl group or the like may be selected. In the structural unit represented by formula (NB), a1 is preferably 0 or 1, and more preferably 0.

[0064] When the polymer P(I) contains a structural unit represented by formula (NB), the proportion of the structural unit represented by formula (NB) in the total structural units constituting the polymer (I) is preferably 10 to 65 mol%, more preferably 12.5 to 60 mol%, and even more preferably 15 to 50 mol%. The structural unit represented by formula (NB) is chemically robust. Therefore, a polymer containing this as a part of the structural unit is stable with a small weight loss when subjected to heat treatment. On the other hand, a polymer containing such a structural unit represented by formula (NB) may have poor alkali solubility. When the polymer P(I) contains a structural unit represented by formula (NB), the content of the structural unit within the above range allows it to have both high alkali solubility and stability in heat treatment.

[0065] In the structural unit represented by formula (ST) which 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 R include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. 40 , R 41 and R 42 is preferably a hydrogen atom.

[0066] R in formula (ST) 43 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above group include substituted or unsubstituted, linear or branched alkyl groups having 1 to 30 carbon atoms, and more specific examples thereof include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxy 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, and a decyl group.

[0068] Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, 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.

[0069] 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. 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, a sec-butoxy group, an isobutoxy group, a tert-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.

[0070] R in the structural unit represented by formula (ST) 43 is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. In addition, R 43 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, R 43 As the organic group having 1 to 30 carbon atoms, a fluorinated alkyl group or the like may be selected.

[0071] When the polymer P(I) contains a structural unit represented by formula (ST), the proportion of the structural unit represented by formula (ST) in all structural units constituting the polymer P(I) is preferably 5 to 30 mol %, more preferably 6 to 28 mol %, and even more preferably 7 to 25 mol %. The structural unit represented by formula (ST) is chemically robust. Therefore, the polymer P(I) containing this structural unit undergoes little weight loss when subjected to heat treatment and is stable. The photosensitive resin composition containing the polymer P(I) containing the structural unit represented by formula (ST) can be suitably used for producing films and filters for use in liquid crystal displays and solid-state imaging devices that require heat resistance. By setting the ratio of the structural unit represented by formula (ST) in the polymer P(I) to the above range, the heat resistance of the polymer P(I) can be improved, and the balance between sensitivity, alkali solubility, and heat discoloration resistance can be improved to a high level.

[0072] When the polymer P(I) contains a structural unit represented by formula (ST), the proportion of the structural unit represented by formula (ST) in all structural units constituting the polymer P(I) is preferably 10 to 45 mol%, more preferably 12.5 to 42.5 mol%, and even more preferably 15 to 40 mol%. By setting the proportion of the structural unit represented by formula (ST) in the polymer P(I) within the above range, it is possible to obtain a polymer P(I) with a highly improved balance of sensitivity, alkali solubility, and heat discoloration resistance.

[0073] In the structural unit represented by formula (MI) which can constitute the polymer P(I), R 32 and R 33 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. 32 and R 33 is preferably a hydrogen atom.

[0074] R in formula (MI) 31 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above group include substituted or unsubstituted, linear or branched alkyl groups having 1 to 30 carbon atoms, and more specific examples thereof include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxy groups.

[0075] 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.

[0076] Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, 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.

[0077] 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. 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, a sec-butoxy group, an isobutoxy group, a tert-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.

[0078] R in the structural unit represented by 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 formula (MI) 31 , R 32 and R 33 By appropriately selecting R 31 By selecting R, the alkali solubility of the resulting polymer P(I) can be adjusted.31 By making R a hydrogen atom, the alkali solubility of the resulting polymer P(I) can be improved. 31 By making M 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 depending on the alkali solubility desired for the application of the polymer P(I). In addition, R 31 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, R 31 As the organic group having 1 to 30 carbon atoms, a fluorinated alkyl group or the like may be selected.

[0079] When the polymer P(I) contains a structural unit represented by formula (MI), the proportion of the structural unit represented by formula (MI) in all structural units constituting the polymer P(I) is preferably 5 to 30 mol%, more preferably 6 to 28 mol%, and further preferably 7 to 25 mol%. By setting the proportion of the structural unit represented by 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.

[0080] The polymer P(I) of the present embodiment may contain a structural unit represented by formula (1-1) in addition to the above structural units.

[0081] [ka]

[0082] 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 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, 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, and a mercapto group. 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, and a mercapto group. When Q is the alkyl group and X is the alkylene group, the alkyl group of Q may be bonded to any carbon atom of the alkylene group of X 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, and a naphthalene ring. In the 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.

[0083] More specifically, 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 represented by the following formula (1a), or an embodiment in which 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.

[0084] [ka]

[0085] In formula (1a), R is a hydrogen atom or a methyl group.

[0086] 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 structural units of the polymer P(I) is preferably 0.5 to 20 mol %, more preferably 1 to 15 mol %.

[0087] The polymer P(I) may contain a structural unit represented by formula (1-4).

[0088] [ka]

[0089] In formula (1-4), R 22 is a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0090] When the polymer P(I) contains a structural unit of the formula (1-1) and a structural unit of the formula (1-4), the polymer P(I) has both a (meth)acryloyl group (the "-Z" group in the formula (1-1)) and a carboxyl group represented by the formula (1-4). This (meth)acryloyl group contains a polymerizable carbon-carbon double bond. In this way, the polymer P(I) can be designed to have a relatively large double bond equivalent and acid value due to the presence of a polymerizable group and a carboxyl group in the same polymer molecule. It is difficult to increase the content of both the polymerizable group and the carboxyl group in other resins such as (meth)acrylic resins. The polymer P can achieve both high sensitivity and developability due to the presence of such a structure.

[0091] The polymer P(I) may contain at least one selected from a structural unit represented by formula (1) and a structural unit represented by formula (2).

[0092] [ka]

[0093] [ka]

[0094] In formula (1) and formula (2), R p and R s , and R 21 and R 22 has the same meaning as in the above formulas (1-1), (1-2) and (1-4).

[0095] When the polymer P(I) contains a structural unit represented by formula (1), the proportion of the structural unit represented by formula (1) in all structural units of the polymer P is preferably 0.5 to 25 mol %, more preferably 1 to 18 mol %.

[0096] When the polymer P(I) contains a structural unit represented by formula (2), the proportion of the structural unit represented by formula (2) in all structural units of the polymer P is preferably 0.5 to 35 mol %, more preferably 2 to 25 mol %.

[0097] The polymer P(I) of the present embodiment may contain a structural unit represented by formula (3) in addition to the above structural units. The polymer P(I) has high alkali solubility due to the structural unit represented by formula (3). As a result, the photosensitive resin composition containing the polymer P(I) has excellent developability when subjected to a photolithography method using an alkaline aqueous solution as a developer. The proportion of the structural unit represented by formula (3) in all structural units of the polymer P(I) is preferably 1 to 10 mol %, more preferably 2 to 7 mol %. [ka]

[0098] The polymer P(I) of the present embodiment may contain a structural unit represented by formula (MA) in addition to the above structural units. The structural unit represented by formula (MA) is ring-opened by an alkaline 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) accounts for preferably 3 to 40 mol %, more preferably 10 to 30 mol %, of all structural units of the polymer P(I).

[0099] The polymer P can include at least one of a structural unit represented by formula (8) and a structural unit represented by formula (9). Here, the structural unit of formula (8) is a structural unit consisting of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-2), and the structural unit of formula (9) is a structural unit consisting of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-3).

[0100] [ka]

[0101] [ka]

[0102] In formula (8), Q, X, and Z are the same as those in formula (1-1), and R p is synonymous with formula (1-2). In formula (9), Z, Q, and X are the same as those in formula (1-1), and R S is synonymous with formula (1-3).

[0103] 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 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 structural units of the polymer P(I) is preferably 0.25 to 17 mol %, more preferably 0.5 to 12 mol %.

[0104] The polymer P(I) may contain a structural unit represented by the following formula (5) which is composed of a structural unit represented by the formula (1-1) and a structural unit represented by the formula (1-4). By containing this structural unit, both the sensitivity and the developability can be achieved in a better balance.

[0105] [ka]

[0106] In formula (5), Z, X, and Q have the same meanings as in formulas (1-1) and (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 structural units of the polymer P(I) is preferably 1 to 12 mol %, more preferably 1 to 9 mol %.

[0107] From the viewpoint of the effects of the present invention, the polymer P(I) may further contain a structural unit represented by the following formula (6) consisting of two structural units represented by the formula (1-1). By containing this structural unit, the sensitivity can be further improved.

[0108] [ka]

[0109] In formula (6), Z, X, and Q have the same meanings as in formula (1-1) and formula (1-4). A plurality of Z's, a plurality of Q's, and a plurality of X's may be the same or different.

[0110] 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 structural units of the polymer P(I) is preferably 1 to 10 mol %, more preferably 1 to 8 mol %.

[0111] The polymer P(I) may comprise a structural unit of formula (MA).

[0112] [ka]

[0113] In formula (MA), R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0114] The structural unit represented by formula (MA) is ring-opened by an alkaline developer to generate two carboxyl groups. Therefore, the polymer P(I) containing the structural unit has excellent developability. When the polymer P(I) contains the structural unit represented by formula (MA), the structural unit represented by formula (MA) is preferably 1 to 35 mol %, more preferably 2 to 30 mol %, of all the structural units of the polymer P(I).

[0115] The content (ratio) of each structural unit contained in the polymer P(I) can be determined by the amount (molar amount) of the raw materials used in synthesizing the polymer, the amount of the raw materials remaining after synthesis, and various spectra (e.g., IR spectrum, 1 H-NMR spectrum, 13 It can be estimated / calculated from the presence and peak area of ​​the C-NMR spectrum.

[0116] The weight average molecular weight Mw of the polymer P(I) is, for example, 3,000 to 50,000. The weight average molecular weight Mw of the polymer P(I) is preferably 3,500 to 45,000, and more preferably 4,000 to 40,000. By appropriately adjusting the weight average molecular weight, it is possible to adjust the sensitivity and the solubility in an alkaline developer. The dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the polymer P(I) of 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 uniform, which is preferable. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0117] The glass transition temperature of the polymer P(I) tends to be low when it contains a structural unit represented by formula (CA), and is preferably 20 to 120° C., more preferably 30 to 110° C. This is preferable in that a pattern formed on a substrate can be stably present when producing a liquid crystal display device or a solid-state imaging device. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0118] The acid value of the polymer P(I) is 60 mgKOH / g or more and 350 mgKOH / g or less, preferably 70 mgKOH / g or more and 300 mgKOH / g or less, and 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 polymer P(I) has an acid value of 60 mgKOH / g or more, good developability can be obtained, and 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.

[0119] If the acid value of the polymer P(I) is too large, the exposed portion may be easily dissolved during development with an alkaline developer, which may increase the amount of exposure required for photocuring or result in an insufficient pattern shape. Therefore, in this embodiment, the upper limit of the acid value is set to 150 mgKOH / g. In addition, 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), the unexposed or low-exposed areas tend to be difficult to dissolve during development with an alkaline developer, and a residual film tends to be generated during development. In addition, if the double bond equivalent is too small, crosslinking causes an excessive increase in molecular weight, which may lead to an excessive decrease in solubility. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 100 g / mol.

[0120] The polymer P(I) of the present embodiment has the above-mentioned constitution, and thus its alkali dissolution rate can be 250 nm / s or more, preferably 350 nm / s or more, more preferably 500 nm / s or more, and particularly preferably 750 nm / s or more. The upper limit is not particularly limited, but may be, for example, 2000 nm / s or less. In the present specification, the alkali dissolution rate is a value measured under the following conditions. (Method of measuring alkaline dissolution rate) Polymer P(I) is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid concentration of 30 mass%. The obtained polymer solution is then spin-coated onto a wafer, the PGMEA is dried, and the wafer is pre-baked at a temperature of 100°C for 2 minutes to prepare a resin film with a thickness of 2 μm ± 0.2. This resin film is immersed together with the wafer in a 2.0 mass% aqueous sodium carbonate solution at a temperature of 23°C. The immersed wafer is visually observed to measure the time until the resin film dissolves and the interference pattern disappears, and the alkaline dissolution rate (μm / sec) is calculated by dividing the film thickness before immersion (2 μm ± 0.2) by this time.

[0121] By adjusting the acid value and / or double bond equivalent of the polymer P(I), it is possible to achieve both sensitivity and developability at a higher level.

[0122] The acid value and double bond equivalent of the polymer P(I) can be determined by spectrum measurement, etc. For example, they can be determined by the following procedure (for more details, see the Examples). (1) Polymer 1From the H-NMR chart, the areas (integral values) of the peaks corresponding to the hydrogen atoms of the carboxyl group and the hydrogen atoms in the vicinity of the polymerizable carbon-carbon double bond are determined. (2) From the area determined in (1) and the area of ​​the peak derived from the standard substance, the amount of carboxyl groups and the amount of carbon-carbon double bonds are calculated. (3) Convert the amount of carboxyl groups obtained in (2) into an acid value (mgKOH / g). Also, convert the amount of polymerizable carbon-carbon double bonds obtained in (2) into a double bond equivalent (g / mol).

[0123] The acid value and double bond equivalent of polymer P(I) can be adjusted to desired values ​​by appropriately designing the ratio of structural units introduced into polymer P(I), in particular 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).

[0124] The content (ratio) of each structural unit contained in the polymer P(I) of the present embodiment can be determined by the amount (molar amount) of the raw material charged during polymer synthesis, the amount of the raw material remaining after synthesis, the peak area of ​​each spectrum (for example, 1 It can be estimated / calculated from the H-NMR peak area, etc.

[0125] (Production method of 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), for convenience, the case where the obtained polymer P(I) is a polymer consisting of a structural unit represented by formula (CA); a structural unit represented by formula (1-2) and / or a structural unit represented by formula (1-3); a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI) is described. Based on the target structure of the polymer P(I), the raw material monomer can be selected. When the polymer P(I) is composed of a structural unit represented by formula (CA) and a structural unit represented by formula (1-2) and / or a structural unit represented by formula (1-3), the raw material monomer represented by formula (CAm) and the raw material monomer represented by formula (MAm) may be used in the step aI described below. Furthermore, for example, when the polymer P(I) contains a structural unit represented by formula (NB), a raw material monomer represented by formula (NBm) may be used in step aI described below. When the polymer P(I) contains a structural unit represented by formula (ST), a raw material monomer represented by formula (STm) may be used in step aI. When the polymer P(I) contains a structural unit represented by formula (MI), a raw material monomer represented by formula (MIm) may be used in step aI.

[0126] Step aI: preparing a raw polymer including a structural unit represented by formula (CA); a structural unit represented by formula (MA); and at least one selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI); Step aII: A step of reacting the raw polymer obtained in step aI with a compound having a hydroxyl group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic compound), and / or a compound having a hydroxyl group and one (meth)acryloyl group (monofunctional (meth)acrylic compound) in the presence of a basic catalyst to prepare a polymer P(I) (sometimes referred to as "polymer precursor (a)") that contains at least one structural unit selected from the structural unit represented by formula (CA); the structural unit represented by formula (1) and / or the structural unit represented by formula (2); the structural unit represented by formula (NB), the structural unit represented by formula (ST), and the structural unit represented by formula (MI), and optionally further contains a structural unit represented by formula (MA). Here, the structural unit represented by formula (1) is a structural unit that contains a structure represented by formula (1-2), and the structural unit of formula (2) is a structural unit that contains a structure represented by formula (1-3).

[0127] When the polymer P(I) (polymer precursor (a)) further comprises a structural unit represented by formula (3), the following step aIII-i is carried out. Step aIII-i: In step aII, a polymer precursor (a) (corresponding to the polymer P(I) in the above step aII) is prepared, which comprises the structural unit represented by formula (CA); the structural unit represented by formula (1) and / or the structural unit represented by formula (2); at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), and the structural unit represented by formula (MI); and the structural unit represented by formula (MA), and then the polymer precursor (a) is treated with water in the presence of a base catalyst to obtain a polymer P(I) (sometimes referred to as "polymer precursor (b)") which comprises the structural unit represented by formula (CA); the structural unit represented by formula (3); the structural unit represented by formula (1) and / or the structural unit represented by formula (2); at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), and the structural unit represented by formula (MI); and optionally further the structural unit represented by formula (MA).

[0128] When the polymer P(I) further contains a structural unit represented by formula (1-1), the following step aIII-ii is carried out. Step aIII-ii: preparing a polymer precursor (a) (corresponding to the polymer P(I) in the above step aII) containing the structural unit represented by formula (CA), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), and the structural unit represented by formula (MI), and the structural unit represented by formula (MA) obtained in step aII, and reacting the polymer precursor (a) with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P(I). Here, the polymer P(I) obtained via step aII and the subsequent step aIII-ii may contain structural units represented by formula (8) and / or formula (9).

[0129] Either step aIII-i or step aIII-ii may be carried out. When both steps are carried out, it is preferable to carry out step aIII-ii after step aIII-i. When carrying out step aIII-ii after step aIII-i, step aIII-ii is a step of reacting the polymer precursor (b) obtained in step aIII-i with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P(I) that may contain structural units represented by formula (8) and / or formula (9), structural units represented by formula (5), and structural units represented by formula (6).

[0130] In the case where both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used in step aII, 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.

[0131] Each step will be described below. (Process aI) In step aI, the step of preparing a raw polymer containing a structural unit represented by formula (CA); a structural unit represented by formula (MA); and at least one selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI) can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (CAm); a monomer represented by formula (MAm); and at least one monomer selected from a monomer represented by formula (NBm), a monomer represented by formula (STm), and a monomer represented by formula (MIm). 51 , R 51 , R 52 and R 53 The definition of is the same as that in formula (CA). 21 and R 22 The definition of is the same as that in formula (MA). 1 , R 2 , R 3 and R 4 The definition of a1 is the same as that of formula (NB). 40 , R 41 , R 42 , and R 43 The definition of is the same as that in formula (ST). Also, R in formula (MIm) 31 , R 32 , and R 33 is the same as in formula (MI).

[0132] [ka]

[0133] In the carboxylic acid-containing alkene as a monomer represented by formula (CAm), the stereochemical configuration with respect to the double bond may be either cis or trans. Examples of the carboxylic acid-containing alkene represented by formula (CAm) include linear carboxylic acid-containing alkenes having terminal double bonds such as 3-butenoic acid, 4-pentenoic acid, 7-octenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, and 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, and oleic acid; branched carboxylic acid-containing alkenes having terminal double bonds such as 2-methyl-4-pentenoic acid and 2,2-dimethyl-4-pentenoic acid.

[0134] [ka]

[0135] [ka]

[0136] Examples of the monomer represented by formula (NBm) include norbornene, bicyclo[2.2.1]-hept-2-ene (trivial 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, and 2-acetyl-5-norbornene. In the polymerization, the monomer represented by formula (NBm) may be used alone or in combination of two or more.

[0137] [ka]

[0138] [ka]

[0139] Although there is no limitation on the polymerization method, radical polymerization using a radical polymerization initiator is preferable. As the polymerization initiator, for example, an azo compound, an organic peroxide, etc. can be used. Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN). Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). The polymerization initiator may be used alone or in combination of two or more kinds.

[0140] The solvent used in the polymerization reaction may be, for example, an organic solvent such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, etc. The polymerization solvent may be a single solvent or a mixed solvent.

[0141] The synthesis of the raw material polymer is carried out by dissolving in a solvent a monomer represented by formula (CAm), a monomer represented by formula (MAm), at least one monomer selected from a monomer represented by formula (NBm), a monomer represented by formula (STm), and a monomer represented by formula (MIm), and a polymerization initiator, charging the resulting mixture into a reaction vessel, and then heating the mixture to allow 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 the target raw polymer is a polymer consisting of a structural unit represented by formula (CA) and a structural unit represented by formula (MA), the molar ratio of the monomer represented by formula (CAm) and the monomer represented by formula (MAm) when charged into a reaction vessel is preferably (CAm):(MAm)=0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1:1. When the target raw material polymer is a polymer containing a structural unit represented by formula (CA); a structural unit represented by formula (MA); and at least one selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI), it is preferable to use each monomer in an amount such that the mixing molar ratio of (CAm+NBm+STm):(MAm+MIm)=0.5:1 to 1:0.5, and it is particularly preferable to use each monomer in an amount such that (CAm+NBm+STm):(MAm+MIm)=1:1, from the viewpoint of controlling the molecular structure of the polymer. Through such a process, a "raw polymer" can be obtained. The raw polymer may be any of random copolymers, alternating copolymers, block copolymers, and periodic copolymers. Typically, it is a random copolymer or an alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability.

[0142] After synthesis of the raw polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be carried out. Specifically, the organic phase containing the synthesized raw polymer and low molecular weight components is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol to precipitate the monomer. The precipitate is filtered and dried to increase the purity of the raw polymer.

[0143] (Step aII) In step aII, the raw 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 polymer is ring-opened, and a structural unit represented by formula (1) and / or a structural unit represented by formula (2) is formed, and a polymer precursor containing a structural unit represented by formula (CA); a structural unit represented by formula (1) and / or a structural unit represented by formula (2); at least one structural unit selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI); and optionally a structural unit represented by formula (MA) is obtained. The polymer precursor obtained here can be used as the polymer P (I) of this embodiment, but for convenience of explanation, it is referred to as a polymer precursor.

[0144] More specifically, first, a solution is prepared by dissolving the raw polymer in an appropriate organic solvent. 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), etc. 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.

[0145] In the case of obtaining a polymer precursor containing the structural unit represented by formula (CA); the structural unit represented by formula (1) and the structural unit represented by formula (2); at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), and the structural unit represented by formula (MI); and the structural unit represented by formula (MA), a polyfunctional (meth)acrylic compound is then added to the above solution. Furthermore, a basic catalyst is added. Then, the solution is appropriately mixed to obtain a uniform solution, and a polymer precursor containing at least the structural unit represented by formula (CA); the structural unit represented by formula (1); at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), and the structural unit represented by formula (MI); and the structural unit represented by formula (MA) is obtained (step aII-i).

[0146] Examples of the polyfunctional (meth)acrylic compound that can be used herein include a compound represented by formula (1b-m), a compound represented by formula (1c-m), and a compound represented by formula (1d-m). 1 , X 1 ' and X 2 The definitions and specific embodiments of are the same as those in the above formula (1b). In addition, k, R, and X in formula (1c-m) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific embodiment of are the same as those in the above formula (1c). n and R in formula (1d-m) are the same as those in the above formula (1d).

[0147] [ka]

[0148] [ka]

[0149] [ka]

[0150] Next, the polymer obtained in step aII-i is reacted with a monofunctional (meth)acrylic compound in the presence of a basic catalyst to obtain a polymer precursor containing a structural unit represented by formula (CA); a structural unit represented by formula (1) and a structural unit represented by formula (2); at least one structural unit selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI); and a structural unit represented by formula (MA) (step aII-ii).

[0151] As the basic catalyst, amine compounds and nitrogen-containing heterocyclic compounds 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 catalysts. The amount of the basic catalyst used can be, for example, about 10 to 60 parts by mass per 100 parts by mass of the raw material polymer. Note that if an excessive amount of the basic catalyst is used, the amount of acid required for neutralization increases, and purification may become complicated.

[0152] The solution is heated preferably at 60 to 80° C. for about 3 to 9 hours to open the structural unit of formula (MA) contained in the raw material polymer and form the structural unit of formula (1).

[0153] For example, by adding a monofunctional (meth)acrylic compound having a hydroxyl group to the reaction system during the heating, the structural unit of formula (MA) contained in the raw polymer is ring-opened / the structural unit of formula (2) is formed, and a polymer P(I) having a structural unit represented by formula (2) is produced.

[0154] From the viewpoint of steric hindrance of the reaction, etc., a monofunctional (meth)acrylic compound having a hydroxyl group tends to react more easily with a raw material polymer than a polyfunctional (meth)acrylic compound having a hydroxyl group. Therefore, when preparing a polymer precursor having a structural unit of formula (2), it is preferable not to charge a monofunctional (meth)acrylic compound having a hydroxyl group into the reaction system from the beginning, 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 formula (2a-m). In formula (2a-m), X 10 and R is defined as in formula (2a).

[0155] [ka]

[0156] Specific examples of the compound represented by formula (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, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid.

[0157] When obtaining a polymer precursor containing either a structural unit represented by formula (1) or a structural unit represented by formula (2), only one of step aII-i and step aII-ii may be carried out after step (I).

[0158] (Step aIII-i) When carrying out step aIII-i, a step of treating the polymer precursor obtained in step aII with water in the presence of a basic catalyst is used. Step aIII-i causes the structural unit represented by formula (MA) contained in the polymer precursor obtained in step aII to open rings, forming a structural unit represented by formula (3), and a polymer P(I) containing at least one structural unit selected from the structural unit represented by formula (CA); the structural unit represented by formula (1) and / or the structural unit represented by formula (2); the structural unit represented by formula (NB), the structural unit represented by formula (ST), and the structural unit represented by formula (MI) can be produced. When a part of the structural unit represented by formula (MA) is opened and a part of the structural unit of formula (MA) remains without being opened, the polymer P(I) further contains a structural unit represented by formula (MA).

[0159] The basic catalyst used in step aIII-i includes an amine compound such as triethylamine, pyridine, dimethylaminopyridine, or a nitrogen-containing heterocyclic compound.

[0160] In step aIII-i, water is added to the reaction system containing the polymer precursor obtained in step aII, and the resulting reaction solution is heated, preferably at 60 to 80° C. for about 0.25 to 6 hours, to open the structural unit of formula (MA) contained in this polymer and generate a structural unit represented by formula (3). The basic catalyst may be the catalyst remaining in the reaction system obtained in step aII as it is. Therefore, step aIII-i is preferably carried out in situ by adding water to the reaction mixture obtained in step aII without performing any post-treatment on the reaction mixture obtained in step aII.

[0161] The polymer P(I) of the present embodiment can be obtained by the above steps. From the viewpoint of the effects of the present invention, the following steps may be further appropriately carried out in order to remove unnecessary components other than the desired polymer.

[0162] First, the reaction solution diluted with an organic solvent and to which an acid (such as formic acid) has been added 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.

[0163] The organic solution of the polymer P(I) obtained is purified using the reprecipitation method or the liquid-liquid extraction method. In the reprecipitation method, the organic solution of the polymer P(I) obtained is added to an excess amount of toluene or water to reprecipitate the polymer. The polymer powder obtained by reprecipitation is further washed several times with toluene or water. Furthermore, in order to remove formic acid and the basic catalyst, the obtained polymer powder is washed with ion-exchanged water several times (about 1 to 3 times). The polymer powder washed with ion-exchanged water is dried, for example, at 30 to 60° C. for 16 hours or more to obtain a high-purity polymer. In the liquid-liquid extraction method, water or a mixed solvent 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 the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more, and the organic phase and the aqueous phase are separated, and the aqueous phase is removed. Further, water or a mixed solvent of water and alcohol is added to the organic solution of the polymer after the aqueous phase is removed, and the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more, and the organic phase and the aqueous phase are separated, and the aqueous phase is removed. In this way, an organic solution of the polymer is obtained. If necessary, a step of adding water or a mixed solvent of water and alcohol and removing the aqueous phase may be further performed. When water is used as the extraction solvent for the liquid-liquid extraction, the amount of polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds remaining tends to be large, and when a mixed solvent of water and alcohol is used, the amount of polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds remaining tends to be small. The obtained organic solution of polymer P(I) is concentrated by heating under reduced pressure using a rotary evaporator, and then the final solvent (PGMEA, etc.) is added to dilute the solution, and the polymer solution dissolved in the final solvent can be obtained by repeating this operation. In addition, the polymer may be further purified by reprecipitation after the solvent replacement.

[0164] The polymer solution may contain a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound used in synthesizing the polymer P (I). When the polymer solution contains these (meth)acrylic compounds, the peak area derived from the polyfunctional (meth)acrylic compound relative to the peak area of ​​the polymer P in a gel permeation chromatography (GPC) chart is, for example, 2 to 50%, preferably 3 to 40%, more preferably 4 to 30%, and even more preferably 5 to 20%, and the peak area derived from the monofunctional (meth)acrylic compound relative to the peak area of ​​the polymer P is, for example, 0.5 to 30%, preferably 0.75 to 20%, and more preferably 1 to 10%. As a result, the photosensitive resin composition containing this polymer solution has good alkali solubility and good sensitivity in photolithography.

[0165] (Step aIII-ii) In step aIII-ii, the polymer (polymer precursor (a)) obtained in step aII or the polymer (polymer precursor (b)) obtained in step aIII-i is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst, whereby a structural unit represented by formula (1-1) is formed by the reaction of the carboxyl group of the polymer precursor (a) or (b) with the epoxy group of the epoxy group-containing (meth)acrylic compound, and a polymer P (I) containing a structural unit represented by formula (CA); a structural unit represented by formula (1) and / or a structural unit represented by formula (2); at least one structural unit selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI); and 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 being ring-opened, the polymer P (I) further contains a structural unit represented by formula (MA).

[0166] Step aIII-ii is preferably carried out by additionally adding an epoxy group-containing (meth)acrylic compound to the reaction system containing the polymer precursor (b) obtained in step aIII-i.

[0167] The reaction between the polymer precursor (a) or (b) and the epoxy group-containing (meth)acrylic compound proceeds in the presence of a basic catalyst. The basic catalyst may be the catalyst remaining in the reaction system obtained in step aII. Therefore, step aIII-ii is preferably carried out in situ by adding the epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor obtained in step aII without isolating and purifying the polymer precursor from the reaction mixture containing the polymer precursor obtained in step aII or neutralizing the basic catalyst contained in the mixture.

[0168] Specifically, the reaction solution obtained by adding an epoxy group-containing (meth)acrylic compound to a reaction mixture containing a polymer precursor is heated preferably at 60 to 80°C for about 1 to 9 hours, whereby the carboxyl group of the polymer precursor reacts with the epoxy group of the epoxy group-containing (meth)acrylic compound to form a structural unit represented by formula (1-1), thereby producing polymer P(I).

[0169] Examples of epoxy group-containing (meth)acrylic compounds include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, glycidyl acrylate, and the like, and one or more selected from these can be used.

[0170] The amount of the epoxy group-containing (meth)acrylic compound added is desirably 0.1 to 3.0 mol per 1 mol of the carboxyl group of the polymer precursor.

[0171] When the polymer P(I) is a polymer obtained via the polymer precursor (a), the polymer P(I) contains a structural unit represented by formula (CA); 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).

[0172] When polymer P is a polymer obtained via polymer precursor (b), polymer P contains a structural unit represented by formula (CA); 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).

[0173] After the step aIII-ii, it is preferable to appropriately further carry out the following steps in order to remove unnecessary components other than the desired polymer P(I).

[0174] First, the reaction solution diluted with an organic solvent and to which an acid (e.g., formic acid, citric acid, etc.) has been added 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 polymer P(I) is obtained.

[0175] An excess amount of toluene is added to the obtained organic solution of the polymer P(I) to reprecipitate the polymer P(I), and the polymer powder obtained by the reprecipitation is further washed several times (e.g., twice) with toluene. Furthermore, in order to remove the acid or basic catalyst, the obtained polymer powder is washed with ion-exchanged water several times (for example, three times). The polymer powder washed with ion-exchanged water is dried, for example, at 30 to 60° C. for 16 hours or more, to obtain a high-purity polymer P(I) of this embodiment.

[0176] [Second embodiment] (Polymer P(II)) The polymer P in the second embodiment (hereinafter referred to as "polymer P(II)") contains a structural unit represented by formula (CA); and at least one structural unit selected from the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3) above, and has a structure represented by formula (P2). The polymer P(II) has a structure in which a polymer chain typically composed of structural units A and B is bonded to a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or difunctional or higher functional thiol group-containing compound represented by "Y" in formula (P2). This monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or difunctional or higher functional thiol group-containing compound is typically an organic group having 1 to 30 carbon atoms containing 1 to 6 thioether groups.

[0177] [ka]

[0178] 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 of the n polymer chains in the brackets [ ]; p and q may be the same or different for each of the n polymer chains in the brackets [ ]; p+q=1, p is greater than or equal to 0, and q is greater than or equal to 0; The molar contents of the structural units A and B contained in the polymer are respectively represented by p t and q t 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 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 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 di- or higher-functional thiol group-containing compound, A represents a structural unit represented by formula (CA), B includes at least one structural unit selected from the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), A plurality of As and Bs may be the same or different.

[0179] In one embodiment, the polymer P(II) may further comprise at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), and the structural unit represented by formula (MI), in which case it has a structure represented by formula (P3).

[0180] [ka]

[0181] 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 in each of the n polymer chains in the brackets [ ]; p, q, and r may be the same or different for each of the n polymer chains in the [ ]; p+q+r=1, where p is greater than or equal to 0, q is greater than or equal to 0, and r is greater than or equal to 0; The molar contents of the structural units A, B, and C contained in the polymer are respectively represented by p t , q t , and r t 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 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 more preferably 0.35 to 0.60; r t is greater than 0, preferably 0.05 to 0.70, more preferably 0.06 to 0.65, and more preferably 0.07 to 0.60; 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 di- or higher-functional thiol group-containing compound, A represents a structural unit represented by formula (CA), B includes 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 includes at least one selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI), A plurality of As, Bs, and Cs may be the same or different.

[0182] The polymer P(II) represented by the formula (P2) or (P3) may contain, as the structural unit B, a structural unit represented by the above formula (1-1). The polymer P(II) represented by the formula (P2) or (P3) may contain, as the structural unit B, a structural unit represented by the above formula (1-4). The polymer P(II) represented by formula (P2) or formula (P3) may contain, as the structural unit B, at least one selected from the structural unit represented by formula (1) and the structural unit represented by formula (2). The polymer P(II) represented by the formula (P2) or (P3) may contain, as the structural unit B, a structural unit represented by the above formula (3). The polymer P(II) represented by formula (P2) or formula (P3) may contain, as the structural unit B, at least one selected from the structural unit represented by formula (8) and the structural unit represented by formula (9). The polymer P(II) represented by the formula (P2) or (P3) may contain, as the structural unit B, a structural unit represented by the above formula (5). The polymer P(II) represented by the formula (P2) or (P3) may contain, as the structural unit B, a structural unit represented by the above formula (6). The polymer P(II) represented by the formula (P2) or (P3) may contain, as the structural unit B, a structural unit represented by the above formula (MA).

[0183] In the formula (P2) or (P4), X is hydrogen or an organic group having 1 to 30 carbon atoms. The organic group having 1 to 30 carbon atoms is R 31 is the same as the organic group having 1 to 30 carbon atoms constituting the above.

[0184] In formula (P2) or formula (P3), Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or difunctional or higher functional thiol group-containing compound (referred to as "organic group (i)" in this specification). In this embodiment, the valency is the number of functional groups (the number of thiol groups). That is, a monofunctional or difunctional or higher functional thiol group-containing compound contains one or more thiol groups, and the organic group (i) bonds to the structural unit in [ ]n and the structural unit in [ ]m via 1 to 6 thioether groups derived from the thiol group. The organic group (i) may have a thiol group that is not involved in the bond with the structural unit in [ ]n and the structural unit in [ ]m, and the polymer P (I) can be obtained as a mixture of resins having a number (n+m) (number of bonds) of 1 to 6. The organic group (i) having 1 to 30 carbon atoms is monofunctional or di- or higher functional, preferably di- or higher functional, more preferably tri- or higher functional. The upper limit is not particularly limited, but is 6 or less functional. The valence of the organic group (i) having 1 to 30 carbon atoms is, for example, monovalent to hexavalent, preferably divalent to hexavalent, and more preferably trivalent to hexavalent, from the viewpoint of the effects of the present invention.

[0185] 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 each having 1 to 6 thioether groups (-S-* (* is a bond)).

[0186] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Examples of alkenyl groups include allyl, pentenyl, and vinyl groups.

[0187] Alkynyl groups include ethynyl groups. 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. Aralkyl groups include, for example, benzyl and phenethyl groups. Examples of the alkaryl group include a tolyl group and a xylyl group.

[0188] Cycloalkyl groups include, for example, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy, isobutoxy, t-butoxy, n-pentyloxy, neopentyloxy, and n-hexyloxy groups. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

[0189] Examples of the monofunctional or difunctional or higher functional thiol group-containing compound from which Y in formula (P2) or formula (P3) can be derived include compounds represented by the following chemical formulas (s-1) to (s-21). That is, "Y" in the polymer P(I) represented by formula (P2) or formula (P3) is a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms derived from a monofunctional or difunctional or higher functional thiol group-containing compound represented by the following:

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193]

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[0194]

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[0195]

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[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203] [ka]

[0204] [ka]

[0205] [ka]

[0206] [ka]

[0207] [ka]

[0208] [ka]

[0209] [ka]

[0210] [ka]

[0211] The difunctional or higher thiol group-containing compound may be used alone or in combination of two or more. Among them, it is preferable to use a trifunctional to hexafunctional (tri- to hexavalent) thiol group-containing compound having 3 to 6 thiol groups in one molecule, because of its excellent reactivity with other monomers. In this embodiment, the monofunctional or di- or higher functional thiol group-containing compound, among the compounds represented by the above formulas (s-1) to (s-21), more preferably includes compounds represented by formulas (s-1) to (s-3), (s-5), and (s-8) to (s-10), and particularly preferably includes compounds represented by 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 its terminal, and bonds to the structural units in [ ]n and [ ]m via the thioether group. The organic group (i) may have a thiol group that is not involved in the bonds with the structural units in [ ]n and [ ]m.

[0212] When the polymer P(II) of the present embodiment has a structure represented by formula (P3) and is obtained by using a tetrafunctional (tetravalent) thiol group-containing compound represented by the above formula (s-2) as a monofunctional or di- or higher functional thiol group-containing compound, the polymer P(II) may have a structure represented by the following formula (I).

[0213] [ka]

[0214] In formula (I), A, B, C, X, p, q, and r have the same meanings as those in formula (P3). However, for the sake of explanation, in formula (I), p, q, and r for each polymer chain in the four brackets [ ] are respectively represented as p 1 ~p 4 , q 1 ~q 4 , r 1 ~r 4 It is written as follows. In formula (I), p 1 ~p 4 , q 1 ~q 4 , r 1 ~r 4 may be the same or different for each polymer chain in the four [ ], and p1 +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. The molar contents of the structural units A, B, and C contained in the polymer represented by formula (I) are respectively represented by p t , q t , and r t Then, 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 It is.

[0215] In formula (I), the order of bonding of A, B, C, and D is not particularly limited, and any of A, B, C, and D may be bonded to a thioether group. In formula (I), an example is shown in which the compound represented by chemical formula (s-2) is bonded to the four structural units in [ ] via thioether groups derived from the four mercapto groups, but the structure may be such that 1 to 3 structural units in [ ] are bonded to the thioether groups derived from the four mercapto groups, and an organic group different from the structural units in [ ] is bonded to the remaining thioether groups. In this embodiment, the polymer P (I) can be obtained as a mixture containing at least one compound to which 1 to 4 structures in [ ] are bonded.

[0216] The physical properties of the polymer P(II) such as the weight average molecular weight Mw, the dispersity (weight average molecular weight Mw / number average molecular weight Mn), the glass transition temperature, the acid value, the double bond equivalent, and the alkali dissolution rate are the same as those of the polymer P(I) described above.

[0217] (Production method of 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), similar to the method for producing the polymer P(I), the obtained polymer P(II) is a polymer having a structure represented by formula (P3), which is composed of at least one selected from the structural unit represented by formula (CA); the structural unit represented by formula (1-2) and / or the structural unit represented by formula (1-3); the structural unit represented by formula (NB), the structural unit represented by formula (ST), and the structural unit represented by formula (MI).

[0218] Step bI: preparing a raw material polymer including a structural unit represented by formula (CA); a structural unit represented by formula (MA); at least one structural unit selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI); and a divalent to hexavalent organic group (i) having 1 to 30 carbon atoms; Step bII: A step of reacting the raw material polymer obtained in step 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 polymer P (II) containing a structural unit represented by formula (CA); a structural unit represented by formula (1) and / or a structural unit represented by formula (2); at least one structural unit selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI); and a divalent to hexavalent organic group (i) having 1 to 30 carbon atoms, and optionally further containing a structural unit represented by formula (MA).

[0219] If the polymer P(II) further comprises a structural unit represented by formula (3), the following step bIII-i is carried out. Step bIII-i: In step bII, a polymer precursor (corresponding to polymer P(II) in the above step bII) is prepared which contains: a structural unit represented by formula (CA); a structural unit represented by formula (1) and / or a structural unit represented by formula (2); at least one structural unit selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI); a divalent to hexavalent organic group (i) having 1 to 30 carbon atoms; and a structural unit represented by formula (MA), and then the polymer precursor is treated with water in the presence of a base catalyst to obtain polymer P(II).

[0220] When the polymer P(II) further contains a structural unit represented by formula (1-1), the following step bIII-ii is carried out. Step bIII-ii: a step of preparing a polymer precursor (corresponding to polymer P(I) in the above step bII) containing the structural unit represented by formula (CA) obtained in step bII; the structural unit represented by formula (1) and / or the structural unit represented by formula (2); at least one structural unit selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), and the structural unit represented by formula (MI); a divalent to hexavalent organic group (i) having from 1 to 30 carbon atoms; and a structural unit represented by formula (MA), and reacting the polymer precursor with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare polymer P(II).

[0221] Either step bIII-i or step bIII-ii may be carried out. When both steps are carried out, it is preferable to carry out step bIII-ii after step bIII-i.

[0222] In the case where both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used in the step bII, it is preferable to first react the polyfunctional (meth)acrylic compound with the raw material polymer obtained in the step bI, and then react the monofunctional (meth)acrylic compound with the obtained reaction mixture.

[0223] Each step will be described below. (Process bI) In step bI, the step of preparing a raw material polymer containing a structural unit represented by formula (CA); a structural unit represented by formula (MA); at least one structural unit selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI); and a divalent 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 (CAm); a monomer represented by formula (MAm); and at least one monomer selected from a monomer represented by formula (NBm), a monomer represented by formula (STm), and a monomer represented by formula (MIm) in the presence of a difunctional or higher thiol group-containing compound.

[0224] Examples of bifunctional or higher thiol group-containing compounds include, but are not limited to, the compounds represented by the above formulas (s-1) to (s-21). The bifunctional or higher thiol group-containing compounds may be used alone or in combination of two or more. The specific conditions for step bI are the same as those for step aI in the production method for the polymer P(I) of the first embodiment.

[0225] (Step bII) In step bII, the same conditions as in step aII in the production method for the polymer P(I) of the first embodiment can be applied.

[0226] (Step bIII-i) In step bIII-i, the same conditions as in step aIII in the production method for the polymer P(I) of the first embodiment can be applied. (Step bIII-i) In step bIII-ii, the same conditions as in step aIII in the production method of the polymer P(I) in the first embodiment can be applied.

[0227] [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 (CA) and a structural unit represented by formula (MA).

[0228] [ka]

[0229] In formula (CA), X 51 is a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, X 51 is a single bond, R 51 , R 52 and R 53 At least one of R is a linear or branched alkyl group having 2 to 20 carbon atoms; 51 , R 52 and R53 the remainder being a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms; X 51 is a linear or branched alkyl group having 1 to 20 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 20 carbon atoms.

[0230] [ka]

[0231] In formula (MA), R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0232] The polymer P(III) is a raw material polymer used in the production of the polymer P(I) in the first embodiment, and is the polymer obtained in the above step aI.

[0233] The weight average molecular weight Mw of the polymer P(III) is, for example, 2,000 to 30,000. The weight average molecular weight Mw of the polymer P(III) is preferably 2,500 to 25,000, and more preferably 3,000 to 20,000. By appropriately adjusting the weight average molecular weight, it becomes possible to adjust the weight average molecular weight of the polymer P(I) obtained from this polymer P(III), and as a result, it is possible to adjust the sensitivity of the polymer P(I) and the solubility in an alkaline developer to a desired level. The dispersity of the polymer P(III) (weight average molecular weight Mw / number average molecular weight Mn) is preferably from 1.0 to 5.0, more preferably from 1.0 to 4.0, and further preferably from 1.0 to 3.0.

[0234] [Fourth embodiment] (Polymer P(IV)) The polymer P in the fourth embodiment (hereinafter referred to as "polymer P(IV)") contains a structural unit represented by formula (CA) and a structural unit represented by formula (MA), and has a structure represented by formula (P2'). The polymer P(IV) has a structure in which a polymer chain typically composed of structural units A and B is bonded to a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or difunctional or higher functional thiol group-containing compound represented by "Y" in formula (P2'). This monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or difunctional or higher functional thiol group-containing compound is typically an organic group having 1 to 30 carbon atoms containing 1 to 6 thioether groups.

[0235] [ka]

[0236] 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 of the n polymer chains in the brackets [ ]; p and q' may be the same or different for each of the n polymer chains in the [ ]; p+q'=1, p is greater than or equal to 0, and q' is greater than or equal to 0; The molar contents of the structural units A and B' contained in the polymer are respectively represented by p t and q t ', 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 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 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 di- or higher functional thiol group-containing compound, A represents a structural unit represented by formula (CA), B' includes at least one structural unit selected from the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), A plurality of A's and B's may be the same or different.

[0237] In one embodiment, polymer P(II) may contain at least one structural unit selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI), and in that case has a structure represented by formula (P3').

[0238] [ka]

[0239] 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 in each of the n polymer chains in the brackets [ ]; p, q', and r may be the same or different for each of the n polymer chains in the [ ]; p+q'+r=1, where p is greater than or equal to 0, q' is greater than or equal to 0, and r is greater than or equal to 0; The molar contents of the structural units A, B', and C contained in the polymer are respectively represented by p t , q t ', and r t 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 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 more preferably 0.35 to 0.60; r t is greater than 0, preferably 0.05 to 0.70, more preferably 0.06 to 0.65, and more preferably 0.07 to 0.60; Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or di- or higher functional thiol group-containing compound, A represents a structural unit represented by formula (CA), B' includes 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 includes at least one selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI), A plurality of A's, B's, and C's may be the same or different.

[0240] The 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 above-mentioned step bI.

[0241] The weight average molecular weight Mw and the dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the polymer P(IV) are the same as those of the polymer P(III) described above.

[0242] [Polymer solution] The polymer solution of this embodiment contains the above-mentioned polymer P(I) or polymer P(II). The polymer solution of this embodiment may contain at least one selected from a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound together with the polymer P(I) or polymer P(II).

[0243] (Polyfunctional (meth)acrylic compounds) The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that can be contained in the polymer solution of this embodiment may be an unreacted (meth)acrylic compound used in the above-mentioned step aII or step bII in the production of polymer P, or may be one that has been added separately.

[0244] Examples of polyfunctional (meth)acrylic compounds that can be incorporated into the polymer solution include, but are not limited to, compounds represented by the following formulas (1b-p), (1c-p), and (1d-p).

[0245] [ka]

[0246] [ka]

[0247] [ka]

[0248] k, R, and X in formula (1b-p) 1 , X 1 ' and X 2 The definitions and specific embodiments of are the same as those in the above formula (1b). In addition, k, R, and X in formula (1c-p) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific embodiments of are the same as those in the above formula (1c).

[0249] In formulae (1b-p), (1c-p) and (1d-p), Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0250] The compounds represented by formula (1b-p), formula (1c-p) and formula (1d-p) in which Y is a hydrogen atom may be unreacted monomers (i.e., compounds represented by formula (1b-p), formula (1c-p) and formula (1d-p)) or may be added separately. In formula (1d-p), n is an integer of 2 or more, preferably an integer of 2 to 5, and more preferably an integer of 2 to 3.

[0251] When a polyfunctional (meth)acrylic compound is blended into the polymer solution of this embodiment in addition to the unreacted 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 attributable to the polyfunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less of the peak area of ​​polymer P(I) or polymer P(II).

[0252] (Monofunctional (meth)acrylic compound) The monofunctional (meth)acrylic compound to be blended in the polymer solution of the present embodiment includes a compound represented by the following formula (2a-m). In formula (2a-m), X 10 and R is defined as in formula (2a).

[0253] [ka]

[0254] When a monofunctional (meth)acrylic compound is blended into the polymer solution of the present embodiment in addition to the unreacted 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 attributable to the monofunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less of the peak area of ​​polymer P(I) or polymer P(II).

[0255] The polymer solution of the present embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. The organic solvent may be one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc.

[0256] 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 is used in such an amount that the concentration of the non-volatile components becomes, for example, 10 to 70% by mass, and preferably 15 to 60% by mass.

[0257] [Preparation of polymer solution] The polymer solution of the present embodiment can be prepared by mixing the above components by a known method. The polymer solution of the present embodiment is used as a resin material for the photosensitive resin composition described below.

[0258] [Photosensitive resin composition] The photosensitive resin composition of the present embodiment includes the above-mentioned polymer P(I) or polymer P(II) and a photopolymerization initiator. That is, the photosensitive resin composition of the present embodiment includes the above-mentioned polymer solution of the present embodiment and a photopolymerization initiator. Each component will be described below.

[0259] (Photopolymerization initiator) The photopolymerization initiator used in the photosensitive resin composition of the present embodiment may be a photoradical polymerization initiator. As the photoradical polymerization initiator, a known compound may be used, for example, 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-methyl ... -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 and other alkylphenone compounds; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone and other benzophenone compounds; benzoin methyl ether, benzoin ethyl benzoin compounds such as benzoin isopropyl ether, benzoin isobutyl ether, etc.; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, etc.; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)- halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine and 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, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Biimidazole 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, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, Examples of the photoradical polymerization initiator include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. The photoradical polymerization initiator may be used alone or in combination of two or more kinds. The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, or preferably 3 to 10 parts by mass, relative to 100 parts by mass of polymer P.

[0260] The photosensitive resin composition of the present embodiment contains the above components, and thus has high sensitivity in photolithography processing and excellent alkali solubility, and therefore has excellent developability and processability in photolithography.

[0261] (Coloring agent) In one embodiment, the photosensitive resin composition may contain a colorant. By containing a colorant, the composition can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state image sensor. As the colorant, various pigments or dyes can be used. As the pigment, an organic pigment or an inorganic pigment can be used.

[0262] Examples of organic pigments that can be used include 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, pyrromethene pigments, and dye lake pigments.

[0263] Examples of inorganic pigments that can be used include white pigments and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellow lead, cadmium-based pigments, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

[0264] 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 type of colorant, or may contain two or more types of colorants.

[0265] Colorants (particularly pigments) having an appropriate average particle size can be used depending on the purpose and application. When transparency is required, such as in color filters, a small average particle size of 0.1 μm or less is preferred, while when hiding properties are required, such as in paints, a large average particle size of 0.5 μm or more is preferred.

[0266] Depending on the purpose and use, 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.

[0267] When the photosensitive resin composition contains a colorant, the amount of the colorant may be appropriately set depending on the purpose and use. In order to achieve a balance between the coloring concentration and the dispersion stability of the colorant, the amount of the colorant is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0268] (Surfactant) The photosensitive resin composition of the present embodiment may contain a surfactant, and the surfactant is preferably a nonionic surfactant.

[0269] The inclusion of a nonionic surfactant improves the coatability of the photosensitive resin composition when it is applied onto a substrate to obtain a resin film, making it possible to obtain a coating film of uniform thickness, and also makes it possible to prevent residues and pattern lifting during development of the coating film.

[0270] The nonionic surfactant is, for example, a compound containing a fluorine group (e.g., 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 fluorine-based surfactants include, but are not limited to, 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. When a surfactant is used, the amount of the surfactant added is preferably 0.01 to 10% by weight based on 100 parts by weight of the resin.

[0271] (solvent) The photosensitive resin composition may typically contain a solvent. As the solvent, an organic solvent is preferably used. Specifically, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc. may be used.

[0272] Examples of solvents 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 mixtures thereof. The amount of the solvent used is not particularly limited, but is used in an amount such that the concentration of non-volatile components becomes, for example, 10 to 70% by mass, and preferably 15 to 60% by mass.

[0273] (Light blocking agent) The resin composition of the present embodiment may contain a light-shielding agent. The photosensitive resin composition may contain only one type of light-shielding agent, or may contain two or more types of light-shielding agents.

[0274] When the photosensitive resin composition contains a light-shielding agent, the amount of the light-shielding agent may be appropriately set depending on the purpose and use. In order to achieve a balance between the light-shielding performance and the dispersion stability of the light-shielding agent, the amount of the light-shielding agent is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0275] (Crosslinking agent) The photosensitive resin composition of the present embodiment may contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it is capable of crosslinking the polymer P (capable of chemically bonding with the polymer P) through the action of active chemical species generated from the photopolymerization initiator. The crosslinking agent may form a bond by reacting with itself instead of only chemically bonding with the polymer.

[0276] The crosslinking agent is preferably, for example, 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 fall under the above-mentioned polymer). It is preferable to use a crosslinking agent having the same type of crosslinking group as the crosslinking group (polymerizable double bond) of the polymer in terms of uniform curing property, further improvement of sensitivity, etc. There is no particular upper limit to the number of functions (the number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, and preferably 6 or less.

[0277] Specific examples of crosslinking agents include 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 polyfunctional (meth)acrylates such as 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, and 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, and ethylene oxide-added dipentaerythritol hexavinyl ether; vinyl ether group-containing (meth)acrylic acid esters, such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate; 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, and ethylene oxide-added dipentaerythritol hexaallyl ether; 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, and alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate; Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Polyfunctional urethane (meth)acrylates obtained by reacting polyfunctional isocyanates, such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, with hydroxyl group-containing (meth)acrylic acid esters, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; etc. can be mentioned.

[0278] Of these, 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.

[0279] When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only one type of crosslinking agent, or may contain two or more types of crosslinking agents. When the photosensitive resin composition contains a crosslinking agent, the amount of the crosslinking agent may be appropriately set according to the purpose and use. As an example, the amount of the crosslinking agent may be usually 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, relative to 100 parts by mass of the photosensitive resin.

[0280] (Other additives) The photosensitive resin composition may contain components such as a filler, a binder resin other than the above-mentioned polymer, an acid generator, a heat resistance improver, a developing aid, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, a matting agent, an antifoaming agent, a leveling agent, an antistatic agent, a dispersant, a slip agent, a surface modifier, a thixotropic agent, a thixotropic aid, a silane coupling agent, and a polyhydric phenol compound depending on various purposes and required properties.

[0281] [Application] A patterned film can be obtained by forming a film using the above-mentioned photosensitive resin composition, and then exposing and developing the film to form a pattern. This film is applied to color filters, black matrices, and the like. 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. Then, a liquid crystal display device or a solid-state imaging device equipped with a color filter or a black matrix can be manufactured. A typical procedure for forming a pattern will now be described.

[0282] (Photosensitive resin film formation) For example, the above-mentioned photosensitive resin composition is applied onto any substrate and dried as necessary to obtain a photosensitive resin film.

[0283] The substrate to which the composition is applied is not particularly limited, and examples thereof include glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, and copper-clad laminates. The substrate may be an unprocessed substrate or a substrate having electrodes or elements formed on its surface, and may be surface-treated to improve adhesion.

[0284] The method for applying the photosensitive resin composition is not particularly limited, and may be spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, an inkjet method, or the like.

[0285] The photosensitive resin composition applied onto the substrate is typically dried by heating using a hot plate, hot air, an oven, etc. The heating temperature is usually 80 to 140° C., and preferably 90 to 120° C. The heating time is usually 30 to 600 seconds, and preferably about 30 to 300 seconds.

[0286] The thickness of the photosensitive resin film is not particularly limited and may be adjusted appropriately depending on the pattern to be finally obtained, but is usually 0.5 to 10 μm, preferably 1 to 5 μm. The thickness can be adjusted by the content of the solvent in the photosensitive resin composition, the coating method, etc.

[0287] (exposure) Exposure is typically carried out by applying actinic rays to the photosensitive resin film through an appropriate photomask.

[0288] Examples of actinic rays include X-rays, electron beams, ultraviolet rays, and visible rays. In terms of wavelength, light of 200 to 500 nm is preferred. In terms of pattern resolution and ease of handling, the light source is preferably g-ray, h-ray, or i-ray from a mercury lamp, and particularly preferably i-ray. Two or more light rays may be mixed and used. As the exposure device, a contact aligner, a mirror projection, or a stepper is preferred. The amount of light for exposure may be appropriately adjusted depending on the amount of photosensitizer in the photosensitive resin film, but is, for example, 100 to 500 mJ / cm 2 That's about it.

[0289] After exposure, the photosensitive resin film may be heated again (post-exposure bake) if necessary. The temperature is, for example, 70 to 150° C., and preferably 90 to 120° C. The time is, for example, 30 to 600 seconds, and preferably 30 to 300 seconds. Post-exposure bake promotes the reaction caused by the radicals generated from the photoradical polymerization initiator, and further accelerates the curing reaction.

[0290] (developing) The exposed photosensitive resin film can be developed with an appropriate developer to obtain a pattern, and a substrate having a pattern can be produced. A photosensitive resin film made of a photosensitive resin composition containing the polymer solution of this embodiment has excellent adhesion to a substrate, and therefore peeling of the pattern is suppressed during the development process.

[0291] In the development step, development can be carried out using an appropriate developer, for example, by a dipping method, a paddle method, a rotary spray method, etc. By development, the exposed area (in the case of a positive type) or the unexposed area (in the case of a negative type) of the photosensitive resin film is dissolved and removed, thereby obtaining a pattern. There is no particular limitation on the type of developer that can be used, and for example, an alkaline aqueous solution or an organic solvent can be used.

[0292] Specific examples of the alkaline aqueous solution include: (i) aqueous inorganic alkaline solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) aqueous organic amine solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine; and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. The polymer of the present embodiment has adjusted alkali solubility and excellent sensitivity, and therefore, when a strongly basic developer such as a TMAH (tetramethylammonium hydroxide) solution is used, a pattern after exposure and development can be formed into a designed shape.

[0293] Specific examples of the organic solvent include ketone-based solvents such as cyclopentanone, ester-based solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether-based solvents such as propylene glycol monomethyl ether. The developer may contain, for example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like.

[0294] In this embodiment, it is preferable to use an alkaline aqueous 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 alkaline 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 having a pattern can be manufactured, but various treatments may be carried out after development.

[0295] 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, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.

[0296] The pattern thus obtained may be heated to be sufficiently cured. The heating temperature is typically 150 to 400°C, preferably 160 to 300°C, and 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 performed using a hot plate, an oven, a temperature-programmable heating oven, or the like. The atmospheric gas used in the heat treatment may be air or an inert gas such as nitrogen or argon. Heating may also be performed under reduced pressure. An example of the structure of a liquid crystal display device and / or a solid-state imaging device having a color filter and / or a black matrix is ​​shown in Fig. 1. Although the black matrix may be a black bank, the following describes a liquid crystal display device and / or a solid-state imaging device having a color filter and a black matrix.

[0297] A black matrix 11 and a color filter 12 are formed on a substrate 10. In addition, a protective film 13 and a transparent electrode layer 14 are provided on the black matrix 11 and the color filter 12.

[0298] The substrate 10 is usually made of a material that transmits light, such as glass, polyester, polycarbonate, polyolefin, polysulfone, a polymer of a cyclic olefin, etc. The substrate 10 may be subjected to a corona discharge treatment, an ozone treatment, a chemical treatment, etc., as necessary. The substrate 10 is preferably made of glass. The black matrix 11 is made of, for example, a cured product of a photosensitive resin composition containing a light-shielding agent.

[0299] There are usually three colors, red, green, and blue, for the color filter 12. The color filter 12 is made of a cured product of a photosensitive resin composition containing a coloring agent corresponding to each color.

[0300] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can also be adopted. EXAMPLES

[0301] The compounds used in the examples may be indicated by the following abbreviations or trade names. ·UDE: 10-undecenoic acid PTE: 4-pentenoic acid MAN: Maleic anhydride ·NB: 2-Norbornene ·IN: Inden ST: Styrene HMI: Maleimide · CyHMI: N-cyclohexylmaleimide MEK: Methyl ethyl ketone GMA: Glycidyl methacrylate PEMP: pentaerythritol tetrakis(3-mercaptopropionate), a 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 compound on the left in the mixture based on gas chromatography is approximately 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0302] [ka]

[0303] <Synthesis of raw polymer> (Synthesis of raw polymer 1) In a suitable sized reaction vessel equipped with a stirrer and a condenser, 588.36g (6.0 mol) of maleic anhydride, 564.90g (6.0 mol) of 2-norbornene, and 55.26g (0.24 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed and dissolved in a mixed solvent of 1716.8g of methyl ethyl ketone and 188.3g of toluene to prepare a solution. Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and then the solution was heated at 65°C for 1.5 hours with stirring, and then further heated at 80°C for 6 hours to polymerize the maleic anhydride and 2-norbornene, producing a polymerized solution. The polymerization solution obtained above was dropped into 14230.2 g of methanol to precipitate a white solid. The obtained white solid was further washed with 3557.5 g of methanol and then vacuum dried at a temperature of 120° C. to obtain 1027.2 g of a polymer (raw polymer 1) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 7,200 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.83.

[0304] (Synthesis of raw polymer 2) In a reaction vessel of suitable size equipped with a stirrer and a cooling tube, 122.4g (1.05 mol) of indene (IN), 1376.7g of methyl ethyl ketone, and 9.70g (0.042 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed and placed in the vessel, and stirred and dissolved. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and the vessel was heated. When the internal temperature reached 80°C, 103.2g (1.05 mol) of maleic anhydride was dissolved in 741.30g of MEK, and the solution in which the dissolved oxygen in the system was removed by nitrogen bubbling was added over 3 hours. After that, the vessel was heated at 80°C for 4 hours to polymerize maleic anhydride and indene, and a polymerized solution was produced. 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 320.1 g of a polymer (raw polymer 2) having a structural unit derived from indene and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 9,200 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 2.31.

[0305] (Synthesis of raw polymer 3) XIRAN (registered trademark) 1000 (styrene-maleic anhydride copolymer, (styrene:maleic acid ratio = 1:1), manufactured by Tomoe Engineering Co., Ltd.), which is a copolymer consisting of structural units derived from styrene and structural units derived from maleic anhydride, was prepared and used as raw polymer 3. The weight average molecular weight Mw of the raw material polymer 3 was 6,500, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 2.51.

[0306] (Synthesis of raw polymer 4) In 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, 4.8 mol in terms of 2-norbornene), maleic anhydride (MAN, 470.69 g, 4.8 mol), and 2281.74 g of methyl ethyl ketone (MEK) were added and stirred to dissolve. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and then the mixture was heated. When the internal temperature reached 80°C, a solution of 2,2'-azobisisobutyrate dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601, 44.21 g, 0.19 mol) and PEMP (93.82 g, 0.19 mol) dissolved in 193.4 g of MEK was added over 1 hour. The mixture was then further reacted at 80°C for 7 hours. The reaction mixture was then 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 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 polymer 4) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The resulting Raw Material Polymer 4 was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 3,500 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.62.

[0307] (Confirmation of the thioether structure contained in raw polymer 4) PEMP alone, as shown in the following chemical formula: 13 By C-NMR measurement, peak a derived from carbon a was confirmed at about 19.0 ppm, and peak b derived from carbon b was confirmed at about 62.0 ppm.

[0308] [ka]

[0309] Raw polymer 4 synthesized using PEMP 13 In the C-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 PEMP alone was observed, and no unreacted PEMP remained, confirming that PEMP was incorporated into raw material polymer 4.

[0310] In addition, raw polymer 4 13 In the C-NMR measurement, the peak a derived from carbon a was not confirmed, and instead, a peak c corresponding to thioether (RS-R') appeared at about 28 ppm. The integral value of this peak c was about twice that of peak b, so raw polymer 4 had a skeleton with a thioether group as shown below, and the thiol group had disappeared.

[0311] [ka]

[0312] 13 The conditions for C-NMR measurement are as follows: (Test conditions) The measurement sample was prepared by adding a measurement solvent to a weighed sample to adjust its concentration, and then pouring a specified amount into a sample tube for NMR measurement. Measurement equipment: JEOL JNM-ECA400 superconducting FT-NMR equipment ·Resonance frequency: 100.53MHz Measurement nucleus: 13 C Measurement method: NNE measurement (inverse gate decoupling method) Pulse width: 3.83μsec Pulse repetition time: 30s Number of times accumulated: 4096 ·Measurement temperature: room temperature Measurement solvent: DMSO-d6 (deuterated dimethyl sulfoxide) Sample concentration: 20% (w / v) The amount of sulfur in the obtained polymer was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that sulfur element was present in the polymer. In addition, the peak derived from PEMP disappeared in the GPC measurement of the reaction solution before the addition of methanol, and it was confirmed that PEMP was incorporated into the raw material polymer 4.

[0313] As a result of elemental analysis, the sulfur content in Raw Material Polymer 4 was found to be 2.4 wt %.

[0314] (Synthesis of raw polymer 5) In a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube, 122.4g (1.05 mol) of indene (IN), 131.0g of methyl ethyl ketone, and 3.73g (0.016 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed and placed in the vessel, and stirred and dissolved. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and the vessel was heated. When the internal temperature reached 55°C, 103.2g (1.05 mol) of maleic anhydride and pentaerythritol tetrakis(3-mercaptopropionate) (PEMP, 20.58g, 0.042 mol) were dissolved in 131.02g of MEK, and the solution in which the dissolved oxygen in the system was removed by nitrogen bubbling was added over 3 hours. After that, the vessel was heated at 55°C for another 3 hours to polymerize maleic anhydride and indene, and a polymerized solution was produced. The polymerization solution obtained above was dropped into 2047.94 g of methanol to precipitate a white solid. The obtained white solid was 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 polymer 5) having a structural unit derived from indene and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 8,200 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.41.

[0315] The amount of sulfur in the obtained raw polymer 5 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in the raw polymer 5. In addition, in the GPC measurement of the reaction solution before the dropwise addition of methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0316] (Synthesis of raw polymer 6) In a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 122.40g (1.18mol) of styrene (ST), 115.24g (1.18mol) of maleic anhydride (MA), and 1940.42g of methyl ethyl ketone (MEK) were added and stirred to dissolve. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and then the mixture was heated. When the internal temperature reached 80°C, a solution of 2,2'-azobisisobutyrate dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601, 10.82g, 0.047mol) and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP, 22.97g, 0.047mol) dissolved in MEK 164.49g was added over 1 hour. Then, the mixture was further reacted at 80°C for 7 hours. The reaction mixture was then 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 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 polymer 5) having a structural unit derived from styrene and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 14,600 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 5.11.

[0317] The amount of sulfur in the obtained raw polymer 6 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in the raw polymer 6. In addition, the peak derived from PEMP disappeared in the GPC measurement of the reaction solution before the dropwise addition of methanol, and it was confirmed that PEMP was incorporated into the polymer.

[0318] (Synthesis of raw polymer 7) In a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 112.98g (0.613mol) of 10-undecenoic acid (UDE), 60.12g (0.613mol) of maleic anhydride (MAN), 167.45g of methyl ethyl ketone (MEK), and dimethyl 2,2'-azobisisobutyrate (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601, 5.65g, 0.025mol) were added and stirred to dissolve. Then, the dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated and reacted at 70°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into a mixed solution of 1181.3g of cyclopentyl methyl ether and 590.6g of toluene to precipitate a white solid. The obtained white solid was further washed with a mixed solution of 590.6 g of cyclopentyl methyl ether and 1,181.3 g of toluene, and then vacuum dried at a temperature of 120°C to obtain 100.2 g of a polymer (raw polymer 7) having a structural unit derived from 10-undecenoic acid and a structural unit derived from maleic anhydride. The resulting Raw Material Polymer 7 was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 12,100 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.56.

[0319] (Synthesis of raw polymer 8) In 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, 0.900 mol in terms of 2-norbornene), maleic anhydride (MAN, 110.32 g, 1.125 mol), 41.46 g (0.225 mol) of 10-undecenoic acid (UDE), and 617.56 g of methyl ethyl ketone (MEK) were added and stirred to dissolve. Then, the dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated. When the internal temperature reached 80°C, a solution of 2,2'-azobisisobutyric acid dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601, 10.36 g, 0.045 mol) dissolved in ME52.24 g was added over 1 hour. The reaction was further carried out at 80°C for 7 hours. The reaction mixture was then 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 149.1 g of a polymer (raw polymer 8) having 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 by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 5,100 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.92.

[0320] (Synthesis of raw polymer 9) In a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, maleic anhydride (MAN, 101.31 g, 1.033 mol), 4-pentenoic acid (PTE) 31.66 g (0.310 mol), and methyl ethyl ketone (MEK) 640.59 g were added and stirred to dissolve. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated. When the internal temperature reached 80°C, 2,2'-azobisisobutyric acid dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601, 9.71 g, 0.042 mol), PEMP (20.19 g, 0.041 mol), and a solution of styrene (ST) 75.32 g (0.723 mol) dissolved in MEK 160.15 g were added over 1 hour. The reaction was further carried out at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into 4153.0 g of methanol to precipitate a white solid. The obtained white solid was further washed with 1038.0 g of methanol and then vacuum dried at a temperature of 120° C. to obtain 156.9 g of a polymer (raw polymer 9) having a structural unit derived from 4-pentenoic acid, a structural unit derived from styrene, and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 7,300 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.89.

[0321] The amount of sulfur in the obtained raw polymer 9 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in the raw polymer 9. In addition, in the GPC measurement of the reaction solution before the dropwise addition of methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0322] (Synthesis of raw polymer 10) In 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 (equivalent to 84.75 g, 0.900 mol of 2-norbornene), 294.18 g (3.000 mol) of maleic anhydride (MAN), 90.11 g (0.900 mol) of 4-pentenoic acid (PTE), and 1046.59 g of methyl ethyl ketone (MEK) were added and dissolved by stirring. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and then the mixture was heated. When the internal temperature reached 80°C, 2,2'-azobisisobutyrate dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601, 24.04g, 0.104mol), styrene (ST) 124.98g (1.200mol), and a solution of PEMP (58.64g, 0.120mol) dissolved in MEK 261.65g were added over 1 hour. The reaction was further carried out at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was added dropwise to 8053.0g of methanol to precipitate a white solid. The obtained white solid was further washed with 2013.0 g of methanol and then vacuum dried at a temperature of 120°C to obtain 420.2 g of a polymer (raw polymer 10) having a structural unit derived from 2-norbornene, a structural unit derived from styrene, a structural unit derived from 4-pentenoic acid, and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 5,500 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.64.

[0323] The amount of sulfur in the obtained raw polymer 10 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in the raw polymer 10. In addition, in the GPC measurement of the reaction solution before the dropwise addition of methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0324] (Synthesis of raw material polymer 11) In a reaction vessel equipped with a stirrer, a cooling tube, and a dropping funnel, 60.78g (0.620 mol) of maleic anhydride (MAN), 31.66g (0.310 mol) of 4-pentenoic acid (PTE), 40.11g (0.413 mol) of maleimide (HMI), and 639.28g of methyl ethyl ketone (MEK) were added and stirred to dissolve. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and the system was heated. When the internal temperature reached 80°C, a solution of 2,2'-azobisisobutyric acid dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601, 9.71g, 0.042mol), styrene (ST) 75.32g (0.723mol), and PEMP (20.19g, 0.041mol) dissolved in MEK 159.82g was added over 1 hour. The reaction was further carried out at 80° C. for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into 4145.0 g of methanol to precipitate a white solid. The obtained white solid was further washed with 1036.0 g of methanol and then vacuum dried at a temperature of 120° C. to obtain 143.7 g of a polymer (raw polymer 11) having a structural unit derived from styrene, a structural unit derived from 4-pentenoic acid, a structural unit derived from maleimide, and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 7,200 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.73.

[0325] The amount of sulfur in the obtained raw polymer 11 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in the raw polymer 11. In addition, in the GPC measurement of the reaction solution before the dropwise addition of methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0326] (Synthesis of raw polymer 12) In 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, 0.900 mol in terms of 2-norbornene), maleic anhydride (MAN, 110.32 g, 1.125 mol), 41.46 g (0.225 mol) of 10-undecenoic acid (UDE), and 597.10 g of methyl ethyl ketone (MEK) were added and stirred to dissolve. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated. When the internal temperature reached 80°C, a solution of 2,2'-azobisisobutyric acid dimethylate (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601, 10.36 g, 0.045 mol) and PEMP (21.99 g, 0.045 mol) dissolved in 50.51 g of MEK was added over 1 hour. The reaction was further carried out at 80° C. for 7 hours. The reaction mixture was then 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 polymer 12) having 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 by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 3,200 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.66.

[0327] The amount of sulfur in the obtained raw polymer 12 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in the raw polymer 12. In addition, in the GPC measurement of the reaction solution before the dropwise addition of methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0328] (Synthesis of raw polymer 13) In the same manner as in Raw Polymer 12, except that 22.53 g (0.225 mol) of 4-pentenoic acid was used instead of 10-undecenoic acid, 162.5 g of a polymer (Raw Polymer 13) having structural units derived from 2-norbornene, structural units derived from 4-pentenoic acid, and structural units derived from maleic anhydride was obtained. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 2,700 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.96.

[0329] The amount of sulfur in the obtained raw polymer 13 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in the raw polymer 13. In addition, in the GPC measurement of the reaction solution before the dropwise addition of methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0330] (Synthesis of raw 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 (equivalent to 84.75 g, 0.900 mol of 2-norbornene), 88.25 g (0.900 mol) of maleic anhydride (MAN), 22.53 g (0.225 mol) of 4-pentenoic acid (PTE), 21.84 g (0.225 mol) of maleimide (HMI), and 544.19 g of methyl ethyl ketone (MEK) were added and dissolved by stirring. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and then the mixture was heated. When the internal temperature reached 80°C, 2,2'-azobisisobutyrate dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601, 10.36g, 0.045mol) and PEMP (21.99g, 0.045mol) dissolved in MEK 50.51g were added over 1 hour. The mixture was further reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into 3621.5g of methanol to precipitate a white solid. The obtained white solid was further washed with 905.4g of methanol and then vacuum dried at a temperature of 120°C to obtain 162.5g of a polymer (raw polymer 14) having a structural unit derived from 2-norbornene, a structural unit derived from 4-pentenoic acid, a structural unit derived from maleimide, and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 3,000 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.59.

[0331] The amount of sulfur in the obtained raw polymer 14 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in the raw polymer 14. In addition, in the GPC measurement of the reaction solution before the dropwise addition of methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0332] (Synthesis of raw polymer 15) In 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 (equivalent to 84.75 g, 0.900 mol of 2-norbornene), 100.86 g (1.029 mol) of maleic anhydride (MAN), 38.62 g (0.386 mol) of 4-pentenoic acid (PTE), 46.09 g (0.257 mol) of N-cyclohexylmaleimide (CyHMI), and 689.11 g of methyl ethyl ketone (MEK) were added and dissolved by stirring. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and then the mixture was heated. When the internal temperature reached 80°C, 2,2'-azobisisobutyric acid dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601, 11.84g, 0.051mol) and PEMP (25.13g, 0.051mol) dissolved in MEK 50.51g were added over 1 hour. The mixture was further reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into 3621.5g of methanol to precipitate a white solid. The obtained white solid was further washed with 905.4g of methanol and then vacuum dried at a temperature of 120°C to obtain 183.4g of a polymer (raw polymer 15) having a structural unit derived from 2-norbornene, a structural unit derived from 4-pentenoic acid, a structural unit derived from N-cyclohexylmaleimide, and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 3,100 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.64.

[0333] The amount of sulfur in the obtained raw polymer 15 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in the raw polymer 15. In addition, in the GPC measurement of the reaction solution before the dropwise addition of methanol, the peak derived from PEMP disappeared, confirming that PEMP was incorporated into the polymer.

[0334] (Synthesis of raw polymer 16) 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 (equivalent to 84.75 g, 0.900 mol of 2-norbornene), 82.10 g (0.837 mol) of maleic anhydride (MAN), 27.00 g (0.147 mol) of 10-undecenoic acid (UDE), 20.32 g (0.209 mol) of maleimide (HMI), and 537.4 g of methyl ethyl ketone (MEK) were added and dissolved by stirring. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and then the mixture was heated. When the internal temperature reached 80°C, a solution of 2,2'-azobisisobutyrate dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601, 9.64g, 0.042mol) and PEMP (20.45g, 0.042mol) dissolved in MEK 50.51g was added over 1 hour. The reaction was further carried out at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was dropped into 3621.5g of methanol to precipitate a white solid. The obtained white solid was further washed with 905.4g of methanol and then vacuum dried at a temperature of 120°C to obtain 150.5g of a polymer (raw polymer 16) having a structural unit derived from 2-norbornene, a structural unit derived from 10-undecenoic acid, a structural unit derived from maleimide, and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 3,200 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.60.

[0335] The amount of sulfur in the obtained raw polymer 16 was confirmed by flask combustion and elemental analysis by ion chromatography, and it was confirmed that elemental sulfur was present in the raw polymer 16. In addition, the peak derived from PEMP disappeared in the GPC measurement of the reaction solution before the dropwise addition of methanol, and it was confirmed that PEMP was incorporated into the polymer.

[0336] (Measurement of physical properties of raw polymer) For the raw polymers 7 to 16, 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 polymer. Table 1 below shows the feeding ratio of the monomers used in the synthesis of the raw polymer, the ratio of the monomers introduced into the raw polymer, and the weight average molecular weight (Mw) and dispersity (Mw / Mn) of the raw polymer. The measurement conditions for the gas chromatography measurement are as follows. ·GC device: GC-2030 (Shimadzu Corporation) Carrier gas: N2 Detector: Flame ionization (FID) detector, FID temperature: 300℃ Column: SH-RXi-1HT, inner diameter 0.25, length 30 m, film thickness 0.25 μm (Shimadzu GLC Corporation) Vaporizer temperature: 210℃ Column flow rate: 0.64mL / min Column heating conditions: Hold at 50℃ for 5 min, heat to 300℃ at 20℃ / min, hold at 300℃ for 10 min

[0337] 1 The acid values ​​of the raw material polymers 7 to 16 measured by H-NMR are shown in Table 1 below. 1 It was confirmed by 1 H-NMR measurement that a carboxy group derived from the structural unit represented by formula (CA) was introduced into the raw material polymers 7 to 16.

[0338] The acid value of the polymer was measured by the following method. Approximately 50 mg of polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. This solution was subjected to 1H-NMR measurement using a nuclear magnetic resonance spectrometer JNM-AL300 (JEOL). The amount of carboxyl groups was calculated from the integral value of the H peak (near 12.4 ppm) of the carboxyl group (-COOH) of the polymer, based on the integral value of the 4H peak (near 8.1 ppm) of the phenyl group of dimethyl terephthalate, the internal standard for 1H-NMR measurement. The acid value (mgKOH / g) can then be calculated from this amount. The larger the acid value, the greater the amount of carboxyl groups per unit mass of the polymer.

[0339] [Table 1]

[0340] <Synthesis of polymer P> Polymer P was prepared using the following method.

[0341] (Preparation Example 1) Polymer P1 was prepared by ring-opening the MA unit of raw material polymer 1 with a monofunctional (meth)acrylic compound. The details are described below. First, 18.44 g of MEK was added to 10.00 g of raw polymer 1 (0.052 mol of MA calculated from the amount of raw polymer 1) 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 reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. The polymer was then purified by the following procedure. The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water twice. The reaction product obtained was dried at 40°C for 12 hours. As a result of the above, 9.5 g of polymer P1 was obtained in which the structural units derived from maleic anhydride in raw polymer 1 were ring-opened with 4-HBA. The weight average molecular weight and polydispersity of the obtained polymer P1 were measured by GPC measurement. The results are shown in Table 1. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P1, which confirmed that the obtained polymer P1 did not contain any unreacted monofunctional (meth)acrylic compound.

[0342] (Preparation Example 2) 99.71g of MEK was added to 60g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 38.75g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 3.5 hours to prepare a reaction solution. Next, 9.00 g (0.500 mol) of water was added to the resulting reaction solution without post-treatment, and the mixture was reacted at 70° C. for 0.5 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution and an aqueous citric acid solution to remove the aqueous phase from the reaction solution. The polymer was then purified by the following procedure. The polymer was reprecipitated with an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The reaction product was dried at 40°C for 12 hours. As a result, polymer P2 was prepared by ring-opening the MA units of raw material polymer 1 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The weight average molecular weight and polydispersity of the obtained polymer P2 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 P2, which confirmed that the obtained polymer P2 did not contain any unreacted polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P2 had a structure in which the structural unit derived from maleic anhydride was ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0343] (Preparation Example 3) Polymer P3 was prepared by ring-opening the MA unit of raw material polymer 1 with a monofunctional (meth)acrylic compound. The details are described below. First, 18.44 g of MEK was added to 10.00 g of raw polymer 2 (0.047 mol in terms of MA calculated from the amount of raw 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 mixture was reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. The polymer was then purified by the same reprecipitation method as in Preparation Example 1. As a result of the above, 9.1 g of polymer P3 was obtained in which the structural units derived from maleic anhydride in raw polymer 1 were ring-opened with 4-HBA. The weight average molecular weight and polydispersity of the obtained polymer P3 were measured by GPC measurement. The results are shown in Table 2. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P3, which confirmed that the obtained polymer P3 did not contain any unreacted monofunctional (meth)acrylic compound. 13 C-NMR measurement confirmed that polymer P3 had a structure ring-opened with 4-HBA. Polymer P3 1The introduction ratio (molar ratio) of the compound reacted with the raw material polymer in the overall structure was calculated by H-NMR measurement. The results are shown in Table 2.

[0344] (Preparation Example 4) Polymer P4 was prepared by ring-opening the MA units of raw material polymer 2 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. Details are described below. 99.71g of MEK was added to 60g of raw polymer 2 (0.280 moles of MA calculated from the amount of raw polymer 2) to prepare a solution. Next, 38.75g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. Next, 3.00 g (0.167 mol) of water was added to the resulting reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. The polymer was then purified in the same manner as in Preparation Example 2. As a result of the above, 45.12 g of polymer P4 was obtained by ring-opening the structural units derived from maleic anhydride in raw polymer 2 with A-TMM-3LM-N, 4-HBA and water. By GPC measurement of polymer P4, it was confirmed that the peaks of the polyfunctional (meth)acrylic compound and monofunctional (meth)acrylic compound used disappeared. This confirmed that the obtained polymer P7 did not contain any unreacted (meth)acrylic compound or (meth)acrylic compound without a hydroxyl group. The weight average molecular weight (Mw) and polydispersity (Mw / Mn) of polymer P4 measured by GPC measurement are shown in Table 2. Polymer P4 has a structure in which the ring is opened with A-TMM-3LM-N, 4-HBA and water. 13 Confirmed by C-NMR.

[0345] (Preparation Example 5) Polymer P5 was prepared by ring-opening the MA unit of raw material polymer 3 with a monofunctional (meth)acrylic compound, as described in detail below. First, 18.44 g of MEK was added to 10.00 g of raw polymer 3 (0.049 mol in terms of MA calculated from the amount of raw polymer 3 charged) 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 mixture was reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. The polymer was then purified by the same reprecipitation method as in Preparation Example 1. As a result of the above, 9.1 g of polymer P5 was obtained in which the structural units derived from maleic anhydride in raw polymer 3 were ring-opened with 4-HBA. The weight average molecular weight and polydispersity of the obtained polymer P5 were measured by GPC measurement. The results are shown in Table 2. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P5, which confirmed that the obtained polymer P5 did not contain any unreacted monofunctional (meth)acrylic compound. Polymer P5 1 The introduction ratio (molar ratio) of the compound reacted with the raw material polymer in the overall structure was calculated by H-NMR measurement. The results are shown in Table 2.

[0346] (Preparation Example 6) Polymer P6 was prepared by ring-opening the MA unit of raw material polymer 4 with a monofunctional (meth)acrylic compound. The details are described below. First, 18.44 g of MEK was added to 10.00 g of raw polymer 1 (0.052 mol in terms of MA calculated from the amount of raw polymer 4) 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 mixture was reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. The polymer was then purified by the same reprecipitation method as in Preparation Example 1. As a result of the above, 8.7 g of polymer P6 was obtained in which the structural units derived from maleic anhydride in raw polymer 4 were ring-opened with 4-HBA. The weight average molecular weight and polydispersity of the obtained polymer P6 were measured by GPC measurement. The results are shown in Table 2. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P6, which confirmed that the obtained polymer P6 did not contain any unreacted monofunctional (meth)acrylic compound.

[0347] (Preparation Example 7) Polymer P7 was prepared by ring-opening the MA unit of raw material polymer 4 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The details are described below. First, 99.93 g of MEK was added to 60.00 g of raw polymer 4 (0.312 mol of MA calculated from the amount of raw polymer 4) 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 reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. Next, 3.00 g (0.167 mol) of water was added to the resulting reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. Liquid-liquid extraction and subsequent solvent exchange were then performed as follows. 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 the same procedure was repeated once more. Solvent replacement: The obtained reaction mixture was subjected to solvent removal at 50°C under reduced pressure using a rotary evaporator. When it was confirmed that the solid content of the polymer solution was 27±2% by mass as measured by a heat-drying moisture meter, the solvent removal operation was stopped. After that, PGMEA was added so that the solid content concentration was 18% by mass, and mixed until it was uniform. The solvent was removed at 50°C under reduced pressure in the same manner, and the solid content concentration was adjusted to 27±2% by mass as measured by a heat-drying moisture meter. Then, PGMEA was added so that the solid content concentration was 18% by mass, and the operation of mixing until it was uniform was repeated two more times. After that, the solvent was removed or PGMEA was added so that the solid content concentration was 30±3% by mass, and the operation of stirring until it was uniform was performed. The above operations removed the solvent used in the reaction, and the solvent was replaced with PGMEA. Then, the product was further purified using the following procedure. The polymer was reprecipitated with an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The reaction product was dried at 40°C for 12 hours. The weight average molecular weight and polydispersity of the obtained polymer P7 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 P7, which confirmed that the obtained polymer P7 did not contain any unreacted polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P7 had a structure in which the structural unit derived from maleic anhydride was ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0348] (Preparation Example 8) Polymer P8 was prepared by ring-opening the MA unit of raw material polymer 5 with a monofunctional (meth)acrylic compound, as described in detail below. First, 18.44 g of MEK was added to 10.00 g of raw polymer 5 (0.047 mol in terms of MA calculated from the amount of raw polymer 5 charged) 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 mixture was reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution. The polymer was then purified by the same reprecipitation method as in Preparation Example 1. As a result of the above, 9.1 g of polymer P8 was obtained in which the structural units derived from maleic anhydride in raw polymer 5 were ring-opened with 4-HBA. The weight average molecular weight and polydispersity of the obtained polymer P8 were measured by GPC measurement. The results are shown in Table 2. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P8, which confirmed that the obtained polymer P8 did not contain any unreacted monofunctional (meth)acrylic compound. Polymer P8 1 The introduction ratio (molar ratio) of the compound reacted with the raw material polymer in the overall structure was calculated by H-NMR measurement. The results are shown in Table 2.

[0349] (Preparation Example 9) Polymer P9 was prepared by ring-opening the MA units of raw material polymer 6 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The details are described below. First, 99.71 g of MEK was added to 60.00 g of raw polymer 6 (0.297 mol of MA calculated from the amount of raw polymer 6) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. Next, 3.00 g (0.167 mol) of water was added to the resulting reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours. The reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. The polymer was then purified in the same manner as in Preparation Example 7. As a result of the above, 31.0 g of polymer P9 was obtained by ring-opening the structural units derived from maleic anhydride in raw polymer 5 with A-TMM-3LM-N, 4-HBA, and water. By GPC measurement of the polymer P9, it was confirmed that the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used disappeared, and it was confirmed that the obtained polymer P9 did not contain any unreacted (meth)acrylic compound or any (meth)acrylic compound not having a hydroxyl group.

[0350] (Preparation Example 10) Polymer P10 was prepared by ring-opening the MA units of raw material polymer 7 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The details are described below. First, 200.1g of MEK and 200.1g of dimethylacetamide were added to 60.00g of raw polymer 7 (0.224 moles of MA calculated from the composition ratio calculated from the GC measurement of raw polymer 7) to prepare a solution. Next, 77.49g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. Further, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. Next, 3.00 g (0.167 mol) of water was added to the resulting reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution, and then further purified by the following procedure. The polymer was reprecipitated with excess water. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The reaction product was dried at 40°C for 12 hours. The weight average molecular weight and polydispersity of the obtained polymer P10 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 P10, which confirmed that the obtained polymer P10 did not contain any unreacted polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that the polymer P11 had a structure in which the structural unit derived from maleic anhydride was ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0351] (Preparation Example 11) The MA unit of the raw material polymer 7 was ring-opened with a trifunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound, further ring-opened by adding water, and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to prepare polymer P11. Details are described below. First, 200.1g of MEK and 200.1g of dimethylacetamide were added to 60.00g of raw polymer 7 (0.224 moles of MA calculated from the amount of raw polymer 8 charged) to prepare a solution. Next, 77.49g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. Further, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. Next, 3.00g (0.167 moles) of water was added to the reaction solution obtained without post-treatment, and reacted at a temperature of 70°C for 2 hours. Further, 13.31g (0.094 moles) of GMA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution, and then further purified by the following procedure. The polymer was reprecipitated with excess water. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The reaction product was dried at 40°C for 12 hours. As a result, the structural unit derived from maleic anhydride in the raw polymer 7 was ring-opened with A-TMM-3LM-N, 4-HBA and water, and reacted with GMA to obtain polymer P11. GPC measurement of polymer P11 confirmed the disappearance of peaks of the polyfunctional (meth)acrylic compound and epoxy group-containing (meth)acrylic compound used, which confirmed that the obtained polymer P11 did not contain unreacted (meth)acrylic compound, (meth)acrylic compound without hydroxyl group, or unreacted epoxy group-containing (meth)acrylic compound.

[0352] (Preparation Example 12) Polymer P12 was prepared by ring-opening the MA unit of raw material polymer 7 with a trifunctional (meth)acrylic compound and water. The details are described below. First, 200.1 g of MEK and 200.1 g of dimethylacetamide were added to 60.00 g of raw material polymer 7 (0.224 mol of MA calculated from the amount of raw material polymer 7) 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 mixture was reacted at a temperature of 70° C. for 2 hours. Next, 3.00 g (0.167 mol) of water was added to the resulting reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution, and then further purified by the following procedure. The polymer was reprecipitated with excess water. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The reaction product was dried at 40°C for 12 hours. As a result, polymer P12 was prepared by ring-opening the MA units of raw material polymer 7 with a trifunctional (meth)acrylic compound and water. The weight average molecular weight and polydispersity of the obtained polymer P12 were measured by GPC measurement. The results are shown in Table 2. Furthermore, the disappearance of the peak of the polyfunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P12, which confirmed that the obtained polymer P12 did not contain any unreacted polyfunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P12 had a structure in which the structural unit derived from maleic anhydride was ring-opened with A-TMM-3LM-N and water.

[0353] (Preparation Example 13) Polymer P13 was prepared by ring-opening the MA units of raw polymer 8 with a monofunctional (meth)acrylic compound in the same manner as in Preparation Example 1, except that 10.00 g of raw polymer 8 (0.050 mol in terms of MA calculated from the composition ratio calculated from the GC measurement of raw polymer 8) was used instead of raw polymer 1. The weight average molecular weight and polydispersity of the obtained polymer P13 were measured by GPC measurement. The results are shown in Table 2. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P13, which confirmed that the obtained polymer P13 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P13 had a structure in which structural units derived from maleic anhydride were ring-opened with 4-HBA.

[0354] (Preparation Example 14) A resin mixture (polymer solution P14) containing polymer P14 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. Details are described below. First, 99.93 g of MEK was added to 60.00 g of raw polymer 9 (0.298 mol of MA calculated from the composition ratio calculated from the GC measurement of raw polymer 9) 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 reacted at a temperature of 70° C. for 2 hours. After that, 56.27 g (0.390 mol) of 4-HBA was added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. Next, 3.00 g (0.167 mol) of water was added to the resulting reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous solution of formic acid and an aqueous solution of citric acid to remove the aqueous phase from the reaction solution. Liquid-liquid extraction and subsequent solvent exchange were then performed as follows. Liquid-liquid extraction: The reaction solution was diluted with MEK, then a water / methanol mixed solvent was added and treated to remove the aqueous phase from the reaction solution, and the same procedure was then repeated once more. Solvent replacement: The resulting reaction mixture was subjected to solvent removal at 50°C under reduced pressure using a rotary evaporator. When it was confirmed that the solid content of the polymer solution was 27±2% by mass as measured by a heat-drying moisture meter, the solvent removal operation was discontinued. After that, PGMEA was added so that the solid content was 18% by mass, and mixed until uniform. The same operation was performed to remove the solvent at 50°C under reduced pressure, and the solid content was adjusted to 27±2% by mass as measured by a heat-drying moisture meter. Then, PGMEA was added so that the solid content was 18% by mass, and the operation of mixing until uniform was repeated two more times. After that, the solvent was removed or PGMEA was added so that the solid content was 30±3% by mass, and the mixture was stirred until uniform. The above operation removed the solvent used in the reaction, and the solvent was replaced with PGMEA.

[0355] As a result of the above, polymer P14 was obtained in which the structural units derived from maleic anhydride in raw polymer 9 were ring-opened with A-TMM-3LM-N, 4-HBA, and water, and a resin mixture (polymer solution P14) containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained. The obtained polymer solution P14 was analyzed by gel permeation chromatography to measure the amounts of polymer P14, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P14. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P12 in a gel permeation chromatography (GPC) chart of the resin mixture. The measurement conditions for gel permeation chromatography are as follows. The GPC measurement device used was a Tosoh HLC-8320GPC EcoSEC. The column temperature was set to 40.0°C, and the pump flow rate was set to 0.350 mL / min. Peak position (retention time) Polymer P14: Peak detected before 20 minutes (peak with shorter retention time and larger molecular weight than A-TMM-3LM-N and 4-HBA) A-TMM-3LM-N: Sum of two peaks, 20.0-20.6 minutes and 20.6-21.5 minutes 4-HBA: 21.7 to 22.4 minutes Measurement conditions: Analysis was performed using a differential refractive index detector (RI detector).

[0356] (Preparation Example 15) A resin mixture (polymer solution P15) containing polymer P15 obtained by ring-opening the MA units of raw polymer 10 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared in the same manner as in Preparation Example 14, except that raw polymer 10 (60.00 g, calculated as 0.303 mol in terms of MA from the composition ratio calculated from the GC measurement of raw polymer 10) was used instead of raw polymer 9.

[0357] The obtained polymer solution P15 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 14 to measure the amounts of polymer P15, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P15. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P15 in a gel permeation chromatography (GPC) chart of the resin mixture.

[0358] (Preparation Example 16) A resin mixture (polymer solution P16) containing polymer P16 obtained by ring-opening the MA units of raw polymer 11 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared in the same manner as in Preparation Example 14, except that raw polymer 9 was replaced with raw polymer 11 (60.00 g, calculated as 0.180 mol in terms of MA from the composition ratio calculated from the GC measurement of raw polymer 11).

[0359] The obtained polymer solution P16 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 14 to measure the amounts of polymer P16, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P16. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P16 in a gel permeation chromatography (GPC) chart of the resin mixture.

[0360] (Preparation Example 17) Polymer P17 was prepared by ring-opening the MA units of raw polymer 12 with a monofunctional (meth)acrylic compound in the same manner as in Preparation Example 1, except that 10.00 g of raw polymer 12 (0.046 mol in terms of MA calculated from the composition ratio calculated from the GC measurement of raw polymer 12) was used instead of raw polymer 1. The weight average molecular weight and polydispersity of the obtained polymer P17 were measured by GPC measurement. The results are shown in Table 2. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P17, which confirmed that the obtained polymer P17 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P17 had a structure in which a structural unit derived from maleic anhydride was ring-opened with 4-HBA.

[0361] (Preparation Example 18) A resin mixture (polymer solution P18) containing polymer P18 obtained by ring-opening the MA units of raw polymer 12 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared in the same manner as in Preparation Example 14, except that raw polymer 9 was replaced with raw polymer 12 (60.00 g, calculated as 0.279 mol in terms of MA from the composition ratio calculated from the GC measurement of raw polymer 12).

[0362] The obtained polymer solution P18 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 14 to measure the amounts of polymer P18, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P18. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P18 in a gel permeation chromatography (GPC) chart of the resin mixture.

[0363] (Preparation Example 19) A resin mixture (polymer solution P19) containing polymer P19 obtained by ring-opening the MA units of raw polymer 13 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared in the same manner as in Preparation Example 14, except that raw polymer 13 60.00 g (0.298 mol in terms of MA calculated from the composition ratio calculated from the GC measurement of raw polymer 13) was used instead of raw polymer 9.

[0364] The obtained polymer solution P19 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 14 to measure the amounts of polymer P19, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P19. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P19 in a gel permeation chromatography (GPC) chart of the resin mixture.

[0365] (Preparation Example 20) Polymer P20 was prepared by ring-opening the MA units of raw polymer 12 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water in the same manner as in Preparation Example 7, except that raw polymer 12 (60.00 g, calculated as 0.279 mol in terms of MA from the composition ratio calculated from the GC measurement of raw polymer 12) was used instead of raw polymer 4. 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 structural unit derived from maleic anhydride was ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0366] (Preparation Example 21) Polymer P21 was prepared by ring-opening the MA units of raw polymer 13 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water in the same manner as in Preparation Example 7, except that raw polymer 13 (60.00 g, calculated as 0.298 mol in terms of MA from the composition ratio calculated from the GC measurement of raw polymer 13) was used instead of raw polymer 4. The weight average molecular weight and polydispersity of the obtained polymer P21 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 P21, which confirmed that the obtained polymer P21 did not contain any unreacted polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound. Also 13C-NMR measurement confirmed that polymer P21 had a structure in which the structural unit derived from maleic anhydride was ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0367] (Preparation Example 22) Polymer P22 was prepared by ring-opening the MA units of raw polymer 14 with a monofunctional (meth)acrylic compound in the same manner as in Preparation Example 1, except that 10.00 g of raw polymer 14 (0.043 mol in terms of MA calculated from the composition ratio calculated from the GC measurement of raw polymer 14) was used instead of raw polymer 1. The weight average molecular weight and polydispersity of the obtained polymer P22 were measured by GPC measurement. The results are shown in Table 2. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P22, which confirmed that the obtained polymer P22 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 C-NMR measurement confirmed that polymer P22 had a structure in which the structural unit derived from maleic anhydride was ring-opened with 4-HBA. Polymer P22 1 The introduction ratio (molar ratio) of the compound reacted with the raw material polymer in the overall structure was calculated by H-NMR measurement. The results are shown in Table 2.

[0368] (Preparation Example 23) A resin mixture (polymer solution P23) containing polymer P23 obtained by ring-opening the MA units of raw polymer 14 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared in the same manner as in Preparation Example 14, except that raw polymer 9 was replaced with raw polymer 14, 60.00 g (0.255 mol in terms of MA calculated from the composition ratio calculated from the GC measurement of raw polymer 14).

[0369] The obtained polymer solution P23 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 14 to measure the amounts of polymer P23, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P23. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P23 in a gel permeation chromatography (GPC) chart of the resin mixture.

[0370] (Preparation Example 24) A resin mixture (polymer solution P24) containing polymer P24 obtained by ring-opening the MA units of raw polymer 15 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared in the same manner as in Preparation Example 14, except that raw polymer 15 60.00 g (0.227 mol in terms of MA calculated from the composition ratio calculated from the GC measurement of raw polymer 15) was used instead of raw polymer 9.

[0371] The obtained polymer solution P24 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 14 to measure the amounts of polymer P24, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P24. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P24 in a gel permeation chromatography (GPC) chart of the resin mixture.

[0372] (Preparation Example 25) A resin mixture (polymer solution P25) containing polymer P25 obtained by ring-opening the MA units of raw polymer 16 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water was prepared in the same manner as in Preparation Example 14, except that raw polymer 16 (60.00 g, calculated as 0.247 mol in terms of MA from the composition ratio calculated from the GC measurement of raw polymer 16) was used instead of raw polymer 9.

[0373] The obtained polymer solution P25 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 14 to measure the amounts of polymer P25, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight average molecular weight and polydispersity of polymer P25. The results are shown in Table 2. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P25 in a gel permeation chromatography (GPC) chart of the resin mixture.

[0374] (Physical property evaluation) The acid value and double bond equivalent of each of the polymers P prepared in Preparation Examples 2 to 5, 8, 13, 17, and 20 to 22 were measured by the methods shown below.

[0375] (Acid value) The acid value of the polymer was measured by the following method. Approximately 50 mg of the polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. The solution was analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 H-NMR measurements were performed. 1 The amount of carboxyl groups is calculated from the integral value of the H peak (around 12.4 ppm) of the polymer's carboxyl group (-COOH) using the integral value of the 4H peak (around 8.1 ppm) of the phenyl group of dimethyl terephthalate, the internal standard for H-NMR measurement, as the standard. The acid value (mgKOH / g) can then be calculated from this amount. The higher the acid value, the greater the amount of carboxyl groups per unit mass of polymer. The results are shown in Table 2. When the acid value is 50 gKOH / g or more, it can be considered that the polymer has a carboxy group necessary for the polymer to have sufficient developability.

[0376] (double bond equivalent) The double bond equivalent of the polymer was measured by the following method. As with the above method for measuring acid value, 1 H-NMR was measured. The amount of acryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal (5.6-5.8 ppm, 3H) derived from the acryloyl group in the obtained spectrum chart to the signal (8.1 ppm, 4H) derived from the phenyl group of the internal standard substance, and the amount of methacryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal (5.6-5.8 ppm, 2H) derived from the phenyl group of the internal standard substance to the signal (8.1 ppm, 4H). Here, the signal derived from the methacryloyl group at 6.0-6.1 ppm was small and overlapped with the signal of the acryloyl group, so it was calculated as the signal of the acryloyl group. The amount of double bonds (mol / g) was calculated from the sum of the amount of acryloyl groups (mol / g) and the amount of methacryloyl groups (mol / g) in the calculated polymer, and the double bond equivalent (g / mol) was calculated from the amount of double bonds. The results are shown in Table 2. A smaller double bond equivalent value indicates a larger amount of C=C double bonds per unit mass of the polymer.

[0377] [Table 2]

[0378] [Table 3]

[0379] (Examples 1 to 16, Comparative Examples 1 to 9) In each of the Examples and Comparative Examples, a resin composition was prepared and evaluated for the following items. <Evaluation> [Alkaline dissolution rate of resin composition] Polymers P1 to P13, P17, and P20 to P22 obtained in Preparation Examples 1 to 13, 17, and 20 to 22 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1 to 13, 17, and 20 to 22 having a solid content concentration of 30 mass %. Next, the above resin compositions 1 to 13, 17, 20 to 22 or resin compositions 14 to 16, 18, 19, 20, 23 to 25 consisting of polymer solutions P14 to P16, P18, P19, P20, and P23 to P25 obtained in Preparation Examples 14 to 16, 18, 19, 20, 23 to 25 were spin-coated onto the wafer, the PGMEA was dried, and the wafer was pre-baked at a temperature of 100° C. for 2 minutes to prepare a resin film with a thickness of approximately 2 μm. This resin film was immersed together with the wafer in a 2% aqueous sodium carbonate solution at 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and dividing that time by the film thickness. The results are shown in Table 3. If the alkali dissolution rate is 250 nm / s or higher, it can be used as a photosensitive material without any problems, if it is 350 nm / s or higher, the developability can be considered to be good, if it is 500 nm / s or higher, it can be considered to be better, and if it is 750 nm / s or higher, it can be considered to be particularly good.

[0380] [Sensitivity evaluation 1 of photosensitive resin composition (exposure amount at which the remaining film rate is 90% or more / exposure amount at which the remaining film rate is 95% or more)] First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid content concentration was 30% by mass. Polymers P1 to P13, P17, P20 to P22 (polymers P in Preparation Examples 1 to 13, 17, and 20 to 22, respectively) or resin compositions 14 to 16, 18, 19, 20, and 23 to 25 (polymer solutions P14 to P16, P18, P19, P20, and P23 to P25 in Preparation Examples 14 to 16, 18, 19, 20, and 23 to 25, respectively): 100 parts by mass (Here, resin compositions P14 to P16, P18, P19, P20, and P23 to P25 were weighed out so that the solid content (the total amount of P14 to P16, P18, P19, P20, P23 to P25, and the polyfunctional (meth)acrylic compound) was 100 parts by mass.) Multifunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by mass Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by weight Adhesion aid (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by weight Surfactant (DIC Corporation, F-556): 0.5 parts by weight

[0381] 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 having a thickness of about 3.0 μm (±0.3 μm). This thin film A was irradiated with 100 mJ / cm 2 using a Canon g+h+i line mask aligner (PLA-501F) through a photomask having a gradation of light shielding rate of 1 to 100%. 2 The sample was exposed to g+h+i rays at an exposure dose of 1000 x 1000. After exposure, the thin film is developed in a 2.0 mass% sodium carbonate aqueous solution at 23°C for 60 seconds (immersion with the wafer), resulting in a light exposure of 1 to 100 mJ / cm. 2 Thin film B was obtained by exposure and development at each exposure dose. From the film thicknesses of Thin Film A and Thin Film B obtained by the above method, the remaining film rate was calculated according to the following formula. Remaining film rate (%) = (film thickness of thin film B at each exposure dose / film thickness of thin film A) x 100 The exposure dose at which the residual film ratio was 90% or more was measured as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. The exposure dose at which the residual film ratio was 90% or more was 30 mJ / cm 2 If the intensity is less than 20 mJ / cm, it can be used as a photosensitive composition without any problems. 2 Sensitivity can be considered good if it is below 15 mJ / cm 2Less than 10 mJ / cm is considered better. 2 It can be considered particularly good if:

[0382] The exposure dose at which the residual film ratio was 95% or more was measured as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. The exposure dose at which the residual film ratio was 95% or more was 50 mJ / cm 2 If the intensity is less than 30 mJ / cm, it can be used without problems as a photosensitive composition. 2 Sensitivity is considered good if it is below 20 mJ / cm 2 Less than or equal to 15 mJ / cm2 is considered better. 2 It can be considered particularly good if:

[0383] [Sensitivity evaluation 2 of photosensitive resin composition (film remaining rate after exposure at low exposure dose)] (5mJ / cm 2 (Remaining film rate at exposure dose of The photosensitive resin composition prepared in the above-mentioned Sensitivity Evaluation 1 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 having a thickness of 3.0 μm (±0.3 μm). This thin film A was irradiated with 5 mJ / cm 2 using a Canon g+h+i line mask aligner (PLA-501F) through a photomask having a gradation of light shielding rate of 1 to 100%. 2 The sample was exposed to g+h+i rays at an exposure dose of 1000 x 1000. After exposure, the thin film was developed in a 2.0 mass % aqueous sodium carbonate solution at 23° C. for 60 seconds (immersion with the wafer) to obtain a thin film B. From the film thicknesses of Thin Film A and Thin Film B obtained by the above method, the remaining film rate was calculated according to the following formula. Remaining film rate (%) = (film thickness of thin film B at each exposure dose / film thickness of thin film A) x 100 The results are shown in Table 3. 5mJ / cm 2 It can be considered that the greater the residual film rate at this exposure dose, the more cured the film is at a lower exposure dose, and the better the sensitivity.

[0384] (10mJ / cm 2 (Remaining film rate at exposure dose of The photosensitive resin composition prepared in the above-mentioned Sensitivity Evaluation 1 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 having a thickness of 3.0 μm (±0.3 μm). This thin film A was irradiated with 10 mJ / cm 2 using a Canon g+h+i line mask aligner (PLA-501F) through a photomask having a gradation of light shielding rate of 1 to 100%. 2 The sample was exposed to g+h+i rays at an exposure dose of 1000 x 1000. After exposure, the thin film was developed in a 2.0 mass % aqueous sodium carbonate solution at 23° C. for 60 seconds (immersion with the wafer) to obtain a thin film B. From the film thicknesses of Thin Film A and Thin Film B obtained by the above method, the remaining film rate was calculated according to the following formula. Remaining film rate (%) = (film thickness of thin film B at each exposure dose / film thickness of thin film A) x 100 The results are shown in Table 3. 2 It can be considered that the greater the residual film rate at this exposure dose, the more cured the film is at a lower exposure dose, and the better the sensitivity.

[0385] [Alkaline dissolution rate of photosensitive resin composition (2.0 mass% sodium carbonate aqueous solution)] The photosensitive resin composition prepared in the above-mentioned Sensitivity Evaluation 1 was spin-coated onto a wafer, the PGMEA was dried, and the wafer was pre-baked at a temperature of 100° C. for 2 minutes to produce a resin film with a thickness of approximately 2 μm. This resin film was immersed together with the wafer in a 2% aqueous sodium carbonate solution at 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and dividing that time by the film thickness. The results are shown in Table 3. If the alkali dissolution rate is 900 nm / s or higher, it can be used as a photosensitive material without any problems, if it is 1100 nm / s or higher, the developability can be considered good, if it is 1300 nm / s or higher, the developability can be considered better, and if it is 1500 nm / s or higher, it can be considered particularly good.

[0386] [Yellow Index] The photosensitive resin composition prepared in the above-mentioned Sensitivity Evaluation 1 was spin-coated on Eagle XG glass (manufactured by Corning, thickness 0.5 mm) and baked on a hot plate at 100°C for 120 seconds to obtain a thin film approximately 3.0 μm thick (±0.1 μm). This thin film was irradiated with 100 mJ / cm using a Canon g+h+i line mask aligner (PLA-600F). 2 The sample was exposed to g+h+i rays at an exposure dose of 1000 x 1000. After exposure, the thin film was developed in a 2.0 mass% sodium carbonate aqueous solution at 23°C for 60 seconds (immersion with the wafer), resulting in a 100mJ / cm 2 A thin film was obtained which was exposed and developed at an exposure dose of 100 nm. The thin film was heat-treated in air at 230°C for 30 minutes. After cooling in air at room temperature, the thin film was again heat-treated in air at 230°C for 30 minutes. The same procedure was repeated, and heat treatment in air for 30 minutes was performed three times in total. The yellow index (YI) of the thin film obtained by the above method was measured three times at different measurement points using a color difference meter CR-5 (manufactured by Konica Minolta), and the average value was taken as the YI value. The measurement type was transmission measurement, and uncoated Eagle XG glass (manufactured by Corning, thickness 0.5 mm) was used for 100% calibration. The results are shown in Table 3. If the yellow index is 1.50 or less, it can be used as a photosensitive resin composition, if it is 1.00 or less, it can be considered that the heat discoloration resistance is good, if it is 0.90 or less, it can be considered that the heat discoloration resistance is better, and if it is 0.85 or less, it can be considered that it is particularly good.

[0387] The results of the developability evaluation and the sensitivity evaluation are shown in Table 3.

[0388] [Table 4]

[0389] [Table 5]

[0390] The photosensitive resin compositions of Examples 1 to 3, which contained polymer P having a structural unit represented by formula (CA) and a structural unit represented by formula (MA), but not having a structural unit represented by formula (NB), a unit represented by formula (ST), or a structural unit represented by formula (MI), had a particularly fast alkali dissolution rate and excellent alkali solubility, and had a well-balanced sensitivity and heat discoloration resistance. The photosensitive resin compositions of Examples 4 to 16, which contained polymer P having a structural unit represented by formula (CA), a structural unit represented by formula (MA), and a structural unit represented by formula (NB), a unit represented by formula (ST), or a unit represented by formula (MI), had a well-balanced alkali solubility, sensitivity, and heat discoloration resistance. Furthermore, the photosensitive resin compositions of Examples 5 to 16, which contained polymer P having an organic group derived from a thiol group-containing compound, had a lower yellow index and better heat discoloration resistance than the photosensitive resin compositions of Examples 1 to 4, which contained polymer P not having an organic group derived from a thiol group-containing compound.

[0391] <Production of color filters / spacers> A suitable amount of pigment dispersion NX-061 (green, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was further added to the photosensitive resin compositions prepared in Examples 1 to 16 to prepare colored photosensitive resin compositions. This was formed into a film on a substrate, and then exposed to light and developed with an alkali to form a green color filter. In addition, by using the same company's NX-053 (blue) or NX-032 (red) as the pigment dispersion liquid instead of NX-061, it was possible to form blue or red color filters.

[0392] <Preparation of black matrix> A suitable amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was further added to the photosensitive resin compositions prepared in Examples 1 to 16 to prepare black photosensitive resin compositions. This was applied to a substrate as a film, and then exposed to light and developed with an alkaline solution to form a black matrix. [Explanation of symbols]

[0393] 10 Substrate 11 Black Matrix 12 Color Filters 13 Protective film 14 Transparent electrode layer

Claims

1. A structural unit represented by formula (CA); At least one structural unit selected from the structural unit represented by formula (1) and the structural unit represented by formula (2); and A polymer comprising a structural unit represented by formula (3), 【Chemical 1】 In formula (CA), X ５１ is a single bond or a linear or branched alkylene group having 1 to 20 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 20 carbon atoms, and the remainder of R ５１ , R ５２ and R ５３ are a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, X ５１ When is a linear or branched alkyl group having 1 to 20 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 20 carbon atoms, [Chemical 2] [Chemical Formula 3] In formula (1) and formula (2), Rp is a group having two or more (meth)acryloyl groups, Rs is a group having one (meth)acryloyl group, R21 and R22 are hydrogen atoms, 【Chemical Formula 4】 In formula (3), R21 and R22 are hydrogen atoms, A polymer.

2. The polymer according to claim 1, The polymer further comprises at least one selected from the structural unit represented by formula (NB), the structural unit represented by formula (ST), and the structural unit represented by formula (MI), [Chemical Formula 5] 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 6】 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 7】 In formula (MI), 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. A polymer.

3. The polymer according to claim 1, further comprising at least one 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), [Chemical 8] 【Chemical Formula 9】 In formula (8) and formula (9), R ｐ is a group having two or more (meth)acryloyl groups, R ｓ is a group having one (meth)acryloyl group, R ２１ and R ２２ are hydrogen 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, a single bond, 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, 【Chemical Formula 10】 【Chemical Formula 11】 In formula (5) and formula (6), 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, a single bond, 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, R21 and R22 are hydrogen atoms, a polymer.

4. The polymer according to claim 1, further comprising a structural unit represented by formula (MA), 【Chemical Formula 12】 In formula (MA), R ２１ and R ２２ are hydrogen atoms, polymers.

5. The polymer according to claim 1, The polymer contains the structure represented by the said formula (1), R in the formula (1) above 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); 【Chemical 13】 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 (k + 1)-valent organic group having 1 to 12 carbon atoms, 【Chemical Formula 14】 In formula (1c), k, R, X １ and X ２ are, respectively, R, k, X in formula (1b) １ and X ２ and are synonymous with R, k, X in formula (1b), respectively. 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 each independently represents 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, 【Chemical Formula 15】 In formula (1d), n is an integer from 2 to 5, R is independently a hydrogen atom or a methyl group, a polymer.

6. The polymer according to claim 1, wherein the polymer contains a structural unit represented by the formula (2), R in the formula (2) above ｓ is a group represented by the formula (2a), 【Chemical 16】 In formula (2a), X １０ is a divalent organic group, and R is a hydrogen atom or a methyl group. a polymer.

7. The polymer according to claim 1, wherein the polymer has a structure represented by the formula (P2), 【Chemical 17】 In the formula (P2), n is an integer of 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 content ratios of each of the 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 ｔ is 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 a structural unit represented by the formula (CA), B contains 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 in which a plurality of As and Bs may be the same or different.

8. The polymer according to claim 2, wherein the polymer has a structure represented by the formula (P3), 【Chemical Formula 18】 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, 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 organic group having 1 to 6 valences and 1 to 30 carbon atoms derived from a thiol group-containing compound, A represents a structural unit represented by the formula (CA), B contains at least one structural unit selected from the structural unit represented by the formula (1) and the structural unit represented by the formula (2), C contains at least one selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), and the structural unit represented by the formula (MI), a polymer in which a plurality of As, Bs, and Cs may be the same or different.

9. The polymer according to claim 1, wherein the weight average molecular weight of the polymer is 3,000 or more and 50,000 or less, a polymer.

10. A polymer solution containing the polymer according to any one of claims 1 to 9.

11. The polymer solution according to claim 10, which further contains a polyfunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, or a combination thereof.

12. The polymer solution according to claim 10, which is used for forming a color filter, a black matrix, a spacer, or a partition wall material.

13. A photosensitive resin composition comprising: the polymer according to any one of claims 1 to 9; and a photo radical polymerization initiator.

14. A cured product formed from the photosensitive resin composition according to claim 13.

15. A structural unit represented by formula (CA); and A structural unit represented by formula (MA); wherein the polymer contains: 【Chemical 19】 In formula (CA), X ５１ is a single bond or a linear or branched alkylene group having 1 to 20 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 20 carbon atoms, and the remainder of R ５１ , R ５２ and R ５３ are a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, X ５１ When is a linear or branched alkyl group having 1 to 20 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 20 carbon atoms, 【Chemical 20】 In formula (MA), R ２１ and R ２２ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, a polymer.

16. The polymer according to claim 15, wherein the polymer further contains at least one selected from a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (MI). 【Chemical 21】 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 22】 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 23】 In formula (MI), 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. Polymer

17. The polymer according to claim 15, wherein the polymer has a structure represented by formula (P2'), 【Chemical 24】 In formula (P2'), n is an integer of 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, When the molar contents of each of the 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, 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, A represents the structural unit represented by the above formula (CA), B' represents the structural unit represented by the above formula (MA), wherein when there are a plurality of As or B's, they may be the same or different.

18. The polymer according to claim 16, wherein the polymer has a structure represented by formula (P3'), 【Chemical 25】 In formula (P3'), n is an integer of 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 of the 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 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 a structural unit represented by the formula (CA), B' represents a structural unit represented by the formula (MA), C contains at least one selected from the structural unit represented by the formula (NB), the structural unit represented by the formula (ST), and the structural unit represented by the formula (MI), A plurality of As, B's, and Cs are polymers that may be the same or different from each other.

19. The polymer according to any one of Claims 15 to 18, wherein the weight average molecular weight of the polymer is 2,000 or more and 30,000 or less.

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