Polymers, polymer solutions, photosensitive resin compositions, and cured products

Abstract

To provide a polymer which has good sensitivity, has high alkali solubility, and is reduced in yellowing.SOLUTION: A polymer P includes at least one structural unit selected from a norbornene monomer-derived structural unit, a norbornene monomer-derived structural unit having at least one carboxy group-containing group, a structural unit including two or more (meth)acryloyl groups, and a structural unit including one (meth)acryloyl group, and may further include a maleic acid anhydride-derived structural unit.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] Liquid crystal display devices and solid-state image sensors typically include a color filter, a black matrix, spacers (e.g., photospacers, colored spacers, black spacers), and partition materials (e.g., transparent banks, black banks). The color filter, black matrix, spacers, and partition materials are configured with structures such as colored patterns and protective films formed on a substrate. Among these structures, the most common method for forming colored patterns and protective films is by photolithography using a photosensitive resin composition. Various studies have been conducted on photosensitive resin compositions. For example, Patent Document 1 describes a photosensitive resin composition comprising an alkali-soluble resin having at least one acidic group and two or more different polymerizable unsaturated groups in its side chain, a polymerizable compound, and a photopolymerization initiator. Furthermore, the examples in Patent Document 1 describe the synthesis of a methacrylic acid / allyl methacrylate / glycidyl adduct as the alkali-soluble resin, and the preparation of a photosensitive resin composition using this adduct. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2012 / 147706 [Overview of the project] [Problems that the invention aims to solve]

[0004] Photosensitive resin compositions used to form color filters, black matrices, spacers, or partition materials utilize resins that undergo polymerization reactions and harden upon exposure to light. Color filters, black matrices, spacers, or partition materials are produced by patterning the photosensitive resin composition through exposure and development, followed by hardening. While "increasing sensitivity" may seem like a common challenge for photosensitive resin compositions, the increasing complexity and widespread use of display and imaging devices necessitates even higher levels of sensitivity. Higher sensitivity in a photosensitive resin composition reduces exposure time, improving productivity. Furthermore, photosensitive resin compositions are required to exhibit excellent processability in development processes using alkaline developers. Additionally, the cured product of the photosensitive resin composition is required to possess high transparency. [Means for solving the problem]

[0005] The present inventors have discovered 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 that has good sensitivity, high alkali solubility, and reduced yellowing, leading to the present invention.

[0006] According to the present invention, The structural unit represented by formula (NB), Structural units represented by formula (NC), A structural unit represented by formula (1-2), and at least one structural unit selected from the structural units represented by formula (1-3), A polymer containing, [ka] In equation (NB), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2. [ka] In formula (NC), R 11 , R 12 , R 13 and R 14 at least one of which is a -Z-COOH group, where Z is a single bond, -CH2-, or -(CH2)2-, and the other R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and a 11 is 0, 1, or 2,

Chemical formula

Chemical formula

[0007] Also according to the present invention, a polymer solution containing the above polymer is provided.

[0008] Also according to the present invention, a photosensitive resin composition containing the above polymer solution and a photopolymerization initiator is provided.

[0009] Also according to the present invention, a cured product of the above photosensitive resin composition is provided.

Advantages of the Invention

[0010] According to the present invention, a polymer as a resin material for use in a photosensitive resin composition having good sensitivity, high alkali solubility, thus excellent developability, and reduced yellowing, thus having high heat discoloration resistance, is provided.

Brief Description of the Drawings

[0011] [Figure 1] This is a schematic diagram (cross-sectional view) illustrating an example of the structure of a liquid crystal display device and / or a solid-state image sensor. [Figure 2] This is the 13C-NMR chart of raw material polymer 2. [Figure 3] This is the 13C-NMR chart of raw material polymer 3. [Modes for carrying out the invention]

[0012] Embodiments of the present invention will be described below with reference to the drawings. In all drawings, similar components are denoted by the same reference numerals, and their descriptions are omitted as appropriate. Furthermore, all drawings are for illustrative purposes only. The shapes and dimensional ratios of each component in the drawings do not necessarily correspond to actual articles. In this specification, the notation "a~b" in the description of numerical ranges means "a or more and b or less" unless otherwise specified. For example, "5~90%" means "5% or more and 90% or less".

[0013] In this specification, when a group (atomic group) is not specified as substituted or unsubstituted, it includes both unsubstituted and substituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups.

[0014] In this specification, the term "(meth)acrylic" refers to a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In particular, the term "(meth)acryloyl group" as used herein refers to a concept that encompasses both the acryloyl group represented by -C(=O)-CH=CH2 and the methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0015] [Polymer P] The polymer of the present invention (hereinafter referred to as "polymer P") will now be described. Unless otherwise specified, structural units or compounds represented by the same structural formula have the same definitions across all embodiments, and the same applies to preferred embodiments. (First embodiment) A polymer of the present invention according to the first embodiment (hereinafter referred to as "polymer P(I)") comprises a structural unit represented by formula (NB), a structural unit represented by formula (NC), a structural unit represented by formula (1-2), and at least one structural unit selected from the structural units represented by formula (1-3).

[0016] [ka]

[0017] In equation (NB), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2.

[0018] [ka]

[0019] In formula (NC), R 11 , R 12 , R 13 and R 14 At least one of them is a -Z-COOH group, where Z is a single bond, -CH2-, or -(CH2)2-, and the other R is 11 , R 12 , R 13 and R 14 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and a 11 It is 0, 1, or 2.

[0020] [ka]

[0021] In formula (1-2), R p R is a group having two or more (meth)acryloyl groups, 22 This refers to a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0022] [ka]

[0023] In formula (1-3), R s R is a group having one (meth)acryloyl group, 22 This refers to a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0024] The polymer P(I) of this embodiment has structural units derived from norbornene represented by formula (NB). Structural units derived from norbornene monomer are chemically robust. Therefore, polymer P(I) containing these structural units exhibits little weight loss and is stable when subjected to heat treatment.

[0025] Furthermore, the polymer P(I) of this embodiment includes structural units represented by formula (1-2) and / or structural units represented by formula (1-3). In other words, polymer P(I) includes either one or both of the structural units represented by formula (1-2) and / or the structural units represented by formula (1-3). As a result, the photosensitive resin composition containing polymer P(I) has excellent sensitivity when subjected to photolithography. This is thought 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).

[0026] Furthermore, the polymer P(I) of this embodiment includes a structural unit represented by formula (NC). Here, formula (NC) has at least one carboxyl group-containing group (-Z-COOH group). By having a carboxyl group-containing group, polymer P(I) has improved alkali solubility and reduced heat yellowing.

[0027] A photosensitive resin composition containing polymer P(I) having the above structural units can be suitably used to manufacture films and filters for use in liquid crystal display devices and solid-state image sensors that require heat resistance and resistance to heat-induced yellowing.

[0028] In the structural unit represented by the above formula (NB) that constitutes polymer P(I), R 1 ~R 4 Organic groups having 1 to 30 carbon atoms that can constitute these groups include saturated or unsaturated linear, branched, or cyclic hydrocarbon groups, alkoxy groups, heterocyclic groups, and carboxyl groups. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalyl groups, and cycloalkyl groups.

[0029] 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.

[0030] Examples of alkenyl groups include allyl groups, pentenyl groups, and vinyl groups. Examples of alkynyl groups include the ethynyl group. Examples of alkylidene groups include methylidene groups and ethylidene groups. Examples of aryl groups include tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups.

[0031] Examples of aralkyl groups include the benzyl group and the phenethyl group. Examples of alkalyl groups include tolyl groups and xylyl groups. Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, neopentyloxy, and n-hexyloxy groups. Examples of heterocyclic groups include epoxy groups and oxetanyl groups.

[0032] In the structural unit represented by formula (NB), R 1 , R 2 , R 3 and R 4 Hydrogen or alkyl groups are preferred, with hydrogen being more preferred. Note, 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 fluorine atoms, hydroxyl groups, carboxyl groups, etc. More specifically, R 1 , R 2 , R 3 and R 4 As the organic group having 1 to 30 carbon atoms, alkyl groups such as fluoride may be selected. In the structural unit represented by formula (NB), a1 is preferably 0 or 1, more preferably 0.

[0033] The proportion of the structural unit represented by formula (NB) in the total structural units constituting polymer P(I) is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, and even more preferably 25 to 45 mol%.

[0034] In the structural unit represented by the above formula (NC) that constitutes polymer P(I), R 11 , R 12 , R 13 and R 14 At least one of them is a -Z-COOH group, where Z is a single bond, -CH2-, or -(CH2)2-, and R 11 , R 12 , R 13 and R14 The remaining ones are, independently, hydrogen atoms or organic groups with 1 to 3 carbon atoms, a 11 It is 0, 1, or 2. In one embodiment, R in the structural unit represented by formula (NC) 11 , R 12 , R 13 and R 14 Two of these, preferably one, is a -Z-COOH group, and the remaining two or three are hydrogen atoms or C1-C3 organic groups, preferably hydrogen atoms. Examples of C1-C3 organic groups include C1-C3 alkyl groups such as methyl, ethyl, n-propyl, and isopropyl groups. In the -Z-COOH group, Z is preferably a single bond or -CH2-, more preferably a single bond. In one embodiment, a in the structural unit represented by formula (NC) 11 This is preferably 0 or 1, more preferably 0.

[0035] The proportion of structural units represented by formula (NC) in the total structural units constituting polymer P(I) is preferably 5 to 30 mol%, more preferably 6 to 28 mol%, and even more preferably 7 to 25 mol%. By setting the proportion of structural units represented by formula (NC) in polymer P(I) within the above range, polymer P(I) can be obtained in which the balance of sensitivity, alkali solubility, and heat discoloration resistance is improved to a high degree.

[0036] Polymer P(I) contains structural units comprising two or more (meth)acryloyl groups (-C(=O)-CH=CH2) represented by formula (1-2), or structural units comprising one (meth)acryloyl group represented by formula (1-3), or combinations thereof. By comprising such structural units, polymer P(I) has superior sensitivity in exposure processing.

[0037] In equation (1-2) or equation (1-3), R 22 Organic groups having 1 to 3 carbon atoms that can constitute this include methyl, ethyl, n-propyl, and isopropyl groups.21 and R 22 Preferably, both are hydrogen atoms.

[0038] 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. p By optimizing the number of (meth)acryloyl groups contained in the polymer, the sensitivity of polymer P(I) containing it during exposure treatment can be further increased. Furthermore, it becomes easier to achieve a higher level of compatibility between the sensitivity and alkali solubility of polymer P(I). Additionally, the heat resistance of polymer P(I) can be improved.

[0039] R in formula (1-2) p Preferably, the group is represented by formula (1b), formula (1c), or formula (1d), and includes at least one selected from these. Having such a group tends to make it easier to obtain the various effects described above.

[0040] [ka]

[0041] In formula (1b), k is either 2 or 3. R represents a hydrogen atom or a methyl group, and multiple Rs may be the same or different. X 1 X is a single bond, an alkylene group with 1 to 6 carbon atoms, or a group represented by -ZX- (where Z is -O- or -OCO-, and X is an alkylene group with 1 to 6 carbon atoms), and there are multiple X groups. 1 They may be the same or different. X 1 ' represents a single bond, an alkylene group with 1 to 6 carbon atoms, or a group represented by -X'-Z'- (where X' is an alkylene group with 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2It is an organic group with 1 to 12 carbon atoms and a (k+1) valency. For R, a hydrogen atom is preferred due to further improvements in sensitivity (ease of polymerization), etc. k can be either 2 or 3, but it is preferably 3 from the standpoint of ease of obtaining raw materials and further improvement of sensitivity.

[0042] X 1 If the alkylene group has 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 If it is an alkylene group with 1 to 6 carbon atoms, then X 1 The group is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and even more preferably a -CH2-(methylene group).

[0043] X 1 When the group is represented by -ZX- (where Z is -O- or -OCO- and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group X having 1 to 6 carbon atoms may be linear or branched. The alkylene group of X having 1 to 6 carbon atoms is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and even more preferably -CH2-CH2-(ethylene group) or -CH2-CH(CH3)-.

[0044] X 1 If ' is an alkylene group having 1 to 6 carbon atoms, then the specific form is X 1 It is similar to that. X 1 If ' is a base represented by -X'-Z'-, the specific form of X' is the same as that of X above.

[0045] X 2 As an organic group with 1 to 12 carbon atoms and a (k+1) valency, any group obtained by removing k+1 hydrogen atoms from any organic compound can be cited. Here, "any organic compound" refers to, for example, an organic compound with a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less. X2 is a group obtained by removing (k + 1) hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group obtained by removing (k + 1) hydrogen atoms from a linear hydrocarbon having 1 to 3 carbon atoms. Here, the hydrocarbon may contain an oxygen atom (such as an ether bond or a hydroxy group). Also, the hydrocarbon is preferably a saturated hydrocarbon. In another aspect, X 2 may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure and a group containing a heterocyclic structure (such as an isocyanuric acid structure).

[0046]

Chemical formula

[0047] In formula (1c), k, R, X 1 and X 2 are respectively synonymous with R, k, X 1 and X 2 in formula (1b), and the plurality of Rs may be the same as or different from each other, and the plurality of Xs 1 may be the same as or different from each other. X 3 is a divalent organic group having 1 to 6 carbon atoms. X 4 and X 5 are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms. X 6 is a divalent organic group having 1 to 6 carbon atoms.

[0048] For the specific aspects, preferred aspects, etc. of R, k, X 1 and X 2 they are the same as those described in formula (1b). X 3 and X 6Examples of the divalent organic group having 1 to 6 carbon atoms include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. Here, the hydrocarbon may contain an oxygen atom (e.g., an ether bond or a hydroxy group). The hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 Examples of the divalent organic group having 1 to 6 carbon atoms for 5 include a linear or branched alkylene group. The number of carbon atoms in the linear or branched alkylene group is preferably 1 to 3.

[0049]

Chemical formula

[0050] In formula (1d), n is an integer of 2 to 5, preferably 2 or 3. Specific embodiments, preferred embodiments, etc. of R are the same as those described in formula (1b).

[0051] 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 the structural units of the polymer P(I) is preferably 3 to 40 mol%, more preferably 3 to 30 mol%.

[0052] In the structural unit represented by formula (1-3) that can constitute the polymer P(I), R S is a group containing only one (meth)acryloyl group. In particular, in the design of a normal photosensitive resin composition, when the curability is increased to improve the sensitivity, the curing often proceeds too much and the developability tends to deteriorate. On the other hand, when the developability is improved, the curing often becomes insufficient. Therefore, the polymer P(I) preferably contains either or both of the structural unit represented by formula (1-2) and the structural unit represented by formula (1-3), so that both the sensitivity and the developability can be balanced well.

[0053] R SThis is a group represented, for example, by the following formula (2a).

[0054] [ka]

[0055] In equation (2a), X 10 X is a divalent organic group, and R is either a hydrogen atom or a methyl group. 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. X 10 A preferred divalent organic group is, for example, an alkylene group. Some of the -CH2- groups in this alkylene group may be ether groups (-O-). The alkylene group may be linear or branched, but linear is more preferred.

[0056] X 10 The divalent organic group is more preferably a linear alkylene group having a total of 3 to 6 carbon atoms. 10 Number of carbon atoms (X 10 By appropriately selecting the chain length, the structural unit represented by formula (2) becomes more likely to participate in the crosslinking reaction, thereby increasing sensitivity.

[0057] X 10 The divalent organic group (e.g., alkylene group) may be substituted with any substituent. Examples of substituents include alkyl groups, aryl groups, alkoxy groups, and aryloxy groups. Also, X 10 The divalent organic group may be any group other than an alkylene group. For example, it may be a divalent group formed by linking one or more groups selected from alkylene groups, cycloalkylene groups, arylene groups, ether groups, carbonyl groups, carboxyl groups, etc.

[0058] When polymer P(I) contains structural units represented by formulas (1-3), the proportion of structural units represented by formula (2) in the total structural units of polymer P(I) is preferably 5 to 30 mol%, more preferably 10 to 20 mol%.

[0059] Furthermore, if polymer P(I) contains both structural units represented by formula (1-2) and structural units represented by formula (1-3), the total proportion of structural units represented by formula (1-2) and structural units represented by formula (1-3) in 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 the total structural units constituting polymer P(I).

[0060] The polymer P(I) of this embodiment may include, in addition to the above-mentioned structural units, structural units represented by formula (1-1).

[0061] [ka]

[0062] In the structural unit represented by formula (1-1), R 21 This refers to 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 C1-C6 alkyl group. Examples of this alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl groups. Substituents for substituted C1-C6 alkyl groups include halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, and mercapto groups. X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms. Examples of alkylene groups constituting X include methylene, ethylene, propylene, and butylene groups. Examples of substituents on a substituted alkylene group having 1 to 4 carbon atoms include halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, and mercapto groups. When Q is the alkyl group and X is the alkylene group, the alkyl group of Q and any carbon atom of the alkylene group of X may bond to form a ring. Examples of ring structures include a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, decalin ring, benzene ring, naphthalene ring, and the like. In formula (1-1), the embodiment in which X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group, or the embodiment in which X is an oxygen atom and Z is a (meth)acryloyl group, is preferably used.

[0063] Preferably, X is an alkylene having 1 to 4 carbon atoms and Z is a (meth)acryloyloxy group represented by the following formula (1a), or X is an oxygen atom and Z is a (meth)acryloyl group.

[0064] [ka]

[0065] In formula (1a), R is either a hydrogen atom or a methyl group.

[0066] When polymer P(I) contains structural units represented by formula (1-1), the proportion of structural units represented by formula (1-1) in the total structural units of polymer P(I) is preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%.

[0067] Polymer P(I) may contain structural units represented by formula (1-4).

[0068] [ka]

[0069] In formula (1-4), R 22 This refers to a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0070] When polymer P(I) contains both the structural unit of formula (1-1) and the structural unit of formula (1-4), polymer P(I) will have both a (meth)acryloyl group (the "-Z" group in formula (1-1)) and a carboxyl group represented by formula (1-4). This (meth)acryloyl group contains a polymerizable carbon-carbon double bond. In this way, polymer P(I) can be designed to have relatively large double bond equivalents and acid values ​​because the polymerizable group and the carboxyl group are present within the same polymer molecule. In contrast, it is difficult to increase the content of both polymerizable groups and carboxyl groups in other resins such as (meth)acrylic resins. By having such a structure, polymer P can achieve a high level of both sensitivity and developability.

[0071] The polymer P(I) may contain at least one selected from the structural units represented by formula (1) and the structural units represented by formula (2).

[0072] [ka]

[0073] [ka]

[0074] In equations (1) and (2), R p and R s , and R 21 and R 22 This is equivalent to the one in equations (1-1), (1-2), and (1-4) above.

[0075] When polymer P(I) contains structural units represented by formula (1), the proportion of structural units represented by formula (1) in the total structural units of polymer P is preferably 0.5 to 25 mol%, more preferably 1 to 18 mol%.

[0076] When polymer P(I) contains structural units represented by formula (2), the proportion of structural units represented by formula (2) in the total structural units of polymer P is preferably 0.5 to 35 mol%, more preferably 2 to 25 mol%.

[0077] The polymer P(I) of this embodiment may contain structural units represented by formula (3) in addition to the structural units described above. By containing structural units represented by formula (3), polymer P(I) has high alkali solubility. As a result, the photosensitive resin composition containing polymer P(I) has excellent developability when subjected to a photolithography method using an alkaline aqueous solution as a developer. The proportion of structural units represented by formula (3) in the total structural units of polymer P(I) is preferably 1 to 10 mol%, more preferably 2 to 7 mol%.

[0078] [ka]

[0079] The polymer P(I) of this embodiment may contain structural units represented by formula (MA) in addition to the above-mentioned structural units. The structural units represented by formula (MA) undergo ring-opening with an alkaline developer to produce two carboxyl groups. Therefore, polymer P(I) has excellent developability. When polymer P(I) contains structural units represented by formula (MA), the amount of structural units represented by formula (MA) in the total structural units of polymer P(I) is preferably 3 to 40 mol%, more preferably 10 to 30 mol%.

[0080] Polymer P may contain at least one of the structural units represented by formula (8) and the structural unit represented by formula (9). Here, the structural unit of formula (8) is a structural unit consisting of the structural unit represented by formula (1-1) and the structural unit represented by formula (1-2), and the structural unit of formula (9) is a structural unit consisting of the structural unit represented by formula (1-1) and the structural unit represented by formula (1-3).

[0081] [ka]

[0082] [ka]

[0083] In equation (8), Q, X, and Z are equivalent to those in equation (1-1), and R p This is equivalent to equation (1-2). In equation (9), Z, Q, and X are equivalent to those in equation (1-1), and R S This is equivalent to equation (1-3).

[0084] When polymer P(I) contains structural units represented by formula (8), the proportion of structural units represented by formula (8) to the total structural units of polymer P(I) is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%. When polymer P(I) contains structural units represented by formula (9), the proportion of structural units represented by formula (9) in the total structural units of polymer P(I) is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%.

[0085] Polymer P(I) may contain a structural unit represented by the following formula (5), which consists of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-4). By including this structural unit, a better balance between sensitivity and developability can be achieved.

[0086] [ka]

[0087] In equation (5), Z, X, and Q are equivalent to those in equations (1-1) and (1-4). When polymer P(I) contains structural units represented by formula (5), the proportion of structural units represented by formula (5) in the total structural units of polymer P(I) is preferably 1 to 12 mol%, more preferably 1 to 9 mol%.

[0088] From the viewpoint of the effects of the present invention, polymer P(I) may further contain a structural unit represented by the following formula (6), which consists of two structural units represented by formula (1-1). By including this structural unit, sensitivity can be further improved.

[0089] [ka]

[0090] In equation (6), Z, X, and Q are equivalent to those in equations (1-1) and (1-4). Multiple Zs, multiple Qs, and multiple Xs may be the same or different.

[0091] When polymer P(I) contains structural units represented by formula (6), the proportion of structural units represented by formula (6) in the total structural units of polymer P(I) is preferably 1 to 10 mol%, more preferably 1 to 8 mol%.

[0092] Polymer P(I) may contain structural units represented by formula (MA).

[0093] [ka]

[0094] In formula (MA), R 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0095] The structural unit represented by formula (MA) undergoes ring-opening with an alkaline developer to produce two carboxyl groups. Therefore, polymer P(i) containing this structural unit exhibits excellent developability. When polymer P(I) contains the structural unit represented by formula (MA), the amount of the structural unit represented by formula (MA) in the total structural units of polymer P(I) is preferably 1 to 35 mol%, more preferably 2 to 30 mol%.

[0096] The content (ratio) of each structural unit contained in polymer P(I) depends on the amount (moles) of raw materials used in the synthesis of the polymer, the amount of 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 of peaks in the 1C-NMR spectrum and their peak areas.

[0097] The weight-average molecular weight Mw of polymer P(I) is, for example, 3,000 to 15,000. Preferably, the weight-average molecular weight Mw of polymer P(I) is 3,500 to 12,000, more preferably 4,000 to 10,000. By appropriately adjusting the weight-average molecular weight, the sensitivity and solubility in alkaline developers can be adjusted. Furthermore, the degree of dispersion (weight-average molecular weight Mw / number-average molecular weight Mn) of polymer P(I) in this embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. By appropriately adjusting the degree of dispersion, the physical properties of polymer P can be made homogenized, which is preferable. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0098] The glass transition temperature of polymer P(I) is preferably 100 to 250°C, more preferably 120 to 230°C. Polymer P(I) has a relatively high glass transition temperature due to the inclusion of structural units represented by formula (NB) and formula (NC). This is advantageous in the manufacturing of liquid crystal displays and solid-state image sensors, as it allows for the stable existence of patterns formed on the substrate. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0099] The acid value of polymer P(I) is 60 mg KOH / g or more and 150 mg KOH / g or less, preferably 70 mg KOH / g or more and 140 mg KOH / g or less. The double bond equivalent of 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. By having an acid value of 60 mgKOH / g or higher for polymer P(I), good developability can be obtained. Furthermore, by having a double bond equivalent of 900 g / mol or less, the sensitivity of the photosensitive resin composition containing polymer P(I) can be increased.

[0100] Furthermore, if the acid value of polymer P(I) is too high, there is a concern that the exposed areas may dissolve easily during development with an alkaline developer, leading to an increased exposure amount required for photocuring or an insufficient pattern shape. Therefore, in this embodiment, the upper limit of the acid value is set to 150 mg KOH / g. Furthermore, if the double bond equivalent of polymer P(I) is too small (i.e., if the density of double bonds in the polymer is too high), unexposed or underexposed areas tend to be difficult to dissolve during development with an alkaline developer, and residual film tends to form during development. Also, if the double bond equivalent is too small, the molecular weight may increase excessively due to crosslinking, raising concerns about an excessive decrease in solubility. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 100 g / mol.

[0101] The polymer P(I) of this embodiment, by having the above configuration, can have an alkali dissolution rate of 200 nm / s or more, preferably 300 nm / s or more, more preferably 400 nm / s or more, and particularly preferably 500 nm / s or more. The upper limit is not particularly limited, but may be, for example, 2000 nm / s or less. In this specification, the alkali dissolution rate is the value obtained when measured under the following conditions. (Method for measuring alkali dissolution rate) Polymer P(I) is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid content concentration of 30% by mass. Next, the obtained polymer solution is spin-coated onto a wafer, the PGMEA is dried, and a resin film with a thickness of 2 μm ± 0.2 is prepared by pre-baking at a temperature of 100°C for 2 minutes. This resin film, along with the wafer, is immersed in a 2.0% by mass sodium carbonate aqueous solution at a temperature of 23°C. The immersed wafer is visually observed, and the time until the resin film dissolves and the interference pattern disappears is measured. The alkali dissolution rate (μm / sec) is calculated by dividing the film thickness before immersion (2 μm ± 0.2) by that time.

[0102] By adjusting the acid value and / or double bond equivalent of polymer P(I), it is possible to achieve an even higher level of balance between sensitivity and developability.

[0103] The acid value and double bond equivalent of polymer P(I) can be determined by spectral measurement or other methods. For example, they can be determined by the following procedure (see the examples for more details). (1) Polymer 1 From the 1H-NMR chart, the area (integral value) of the peaks corresponding to hydrogen atoms of the carboxyl group and hydrogen atoms near polymerizable carbon-carbon double bonds is determined. (2) The area obtained in (1) is used to determine the amount of carboxyl groups and carbon-carbon double bonds from the area of ​​the peaks originating from the standard substance. (3) Convert the amount of carboxyl groups obtained in (2) to the acid value (mgKOH / g). Also, convert the amount of polymerizable carbon-carbon double bonds obtained in (2) to the double bond equivalent (g / mol).

[0104] 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), particularly the number of polymerizable carbon-carbon double bonds in the (meth)acryloyl groups contained in the structural units represented by formula (1) or formula (2).

[0105] The content (ratio) of each structural unit contained in polymer P(I) of this embodiment depends on the amount (moles) of raw materials charged during polymer synthesis, the amount of raw materials remaining after synthesis, and the peak areas of various spectra (for example, 1 It can be estimated / calculated from the peak area of ​​the 1H-NMR spectrum, etc.

[0106] (Method for producing polymer P(I)) Polymer P(I) can be manufactured (synthesized) by any method. Typically, polymer P(I) can be manufactured by the following steps aI, aII, and aIII. Step aI: A step of preparing a raw material polymer containing structural units represented by formula (NB), formula (NC), and formula (MA); Step aII: A step in which the raw material polymer obtained in Step aI is reacted with a compound having a hydroxyl group and two or more (meth)acryloyl groups (a polyfunctional (meth)acrylic compound), and / or a compound having a hydroxyl group and one (meth)acryloyl group (a monofunctional (meth)acrylic compound) in the presence of a basic catalyst to prepare polymer P(I) (sometimes referred to as "polymer precursor (a)") which includes a structural unit represented by formula (NB), a structural unit represented by formula (NC), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further including a structural unit represented by formula (MA). Here, the structural unit represented by formula (1) includes the structure of formula (1-2), and the structural unit of formula (2) includes the structure of formula (1-3).

[0107] If polymer P(I) (polymer precursor(a)) further contains structural units represented by formula (3), the following step aIII-i is performed. Step aIII-i: A step in which a polymer precursor (a) (corresponding to polymer P(I) in step aII above) is prepared, comprising a structural unit represented by formula (NB), a structural unit represented by formula (NC), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA); and thereafter, the polymer precursor (a) is treated with water in the presence of a base catalyst to obtain polymer P(I) (sometimes referred to as "polymer precursor (b)") comprising a structural unit represented by formula (NB), a structural unit represented by formula (NC), a structural unit represented by formula (3), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further comprising a structural unit represented by formula (MA).

[0108] If polymer P(I) further contains structural units represented by formula (1-1), the following steps aIII-ii are performed. Step aIII-ii: A step to prepare a polymer precursor (a) (corresponding to polymer P(I) in step aII) obtained in step aII, which contains a structural unit represented by formula (NB), a structural unit represented by formula (NC), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally a structural unit represented by formula (MA), and to prepare polymer P(I) by reacting the polymer precursor (a) with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst. Here, 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).

[0109] Steps aIII-i and aIII-ii may be carried out individually. If both are carried out, it is preferable to carry out step aIII-ii after step aIII-i. If step aIII-ii is carried out 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) which 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).

[0110] In step aII, if both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used, it is preferable to first react the polyfunctional (meth)acrylic compound with the raw material polymer obtained in step aI, and then react the resulting reaction mixture with the monofunctional (meth)acrylic compound.

[0111] The following describes each step. (Process aI) The step in step aI of preparing a raw material polymer containing structural units represented by formula (NB), formula (NC), and formula (MA) can be carried out by polymerizing (addition polymerization) a monomer composition containing monomers represented by formula (NBm), monomers represented by formula (NCm), and monomers represented by formula (MAm). Here, in formula (NBm), R 1 , R 2 , R 3 and R 4 Furthermore, the definition of a1 is the same as that in equation (NB). Also, R in equation (NCm) 11 , R 12 , R 13 and R 14 The definition of is the same as in equation (NC). Also, R in equation (MAm) 21 and R 22 The definition is the same as that in equation (MA).

[0112] [ka]

[0113] Examples of monomers represented by formula (NBm) include norbornene, bicyclo[2.2.1]-hepto-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, and 2-acetyl-5-norbornene. During polymerization, one monomer represented by formula (NBm) may be used, or two or more monomers may be used in combination.

[0114] [ka]

[0115] [ka]

[0116] While the polymerization method is not limited, radical polymerization using a radical polymerization initiator is preferred. Examples of polymerization initiators include azo compounds and organic peroxides. Specific examples of azo compounds include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonile) (ABCN). Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Regarding polymerization initiators, one type may be used, or two or more types may be used in combination.

[0117] For the polymerization reaction, organic solvents such as diethyl ether, tetrahydrofuran, toluene, and methyl ethyl ketone can be used as solvents. The polymerization solvent may be a single solvent or a mixture of solvents.

[0118] The raw material polymer is synthesized by dissolving monomers represented by formula (NBm), (NCm), and (MAm), along with a polymerization initiator, in a solvent, charging the mixture into a reaction vessel, and then heating it to allow addition polymerization to proceed. The heating temperature is, for example, 50-80°C, and the heating time is, for example, 5-20 hours. When charging the reaction vessel, the molar ratio of the total amount of monomers represented by formula (NBm) and (NCm) (NBm + NCm) to the monomer represented by formula (MAm) is preferably (NBm + NCm):(MAm) = 0.5:1 to 1:0.5. From the viewpoint of molecular structure control, a molar ratio of 1:1 is preferable. The molar ratio of monomers represented by formula (NBm) and (NCm) is preferably (NBm):(NCm) = 9.5:0.5 to 2:8, and more preferably 9:1 to 7:3. Through this process, "raw material polymers" can be obtained. The raw material polymer may be any of the following: random copolymer, alternating copolymer, block copolymer, or periodic copolymer. Typically, it is a random copolymer or alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability.

[0119] Furthermore, after the synthesis of the raw material polymer, a step may be taken to remove low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators. Specifically, the organic phase containing the synthesized raw material polymer and low molecular weight components is concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol to precipitate the monomers. By filtering and drying this precipitate, the purity of the raw material polymer can be increased.

[0120] (Step aII) In step aII, the raw material polymer obtained in step aI is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst. This causes some of the structural units represented by formula (MA) in the raw material polymer to open rings, forming structural units represented by formula (1) and / or formula (2). A polymer precursor is obtained that contains structural units represented by formula (NB), structural units represented by formula (NC), and structural units represented by formula (1) and / or formula (2), and optionally contains structural units represented by formula (MA). The polymer precursor obtained here can be used as polymer P(I) in this embodiment, but for the sake of explanation, it is referred to as a polymer precursor.

[0121] More specifically, first, a solution is prepared by dissolving the raw material polymer in a suitable organic solvent. As the organic solvent, single or mixed solvents such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and tetrahydrofuran (THF) can be used, but are not limited to these; various organic solvents used in the synthesis of organic compounds and polymers can be used.

[0122] To obtain a polymer precursor containing structural units represented by formula (NB), structural units represented by formula (NC), and both structural units represented by formula (1) and formula (2), a polyfunctional (meth)acrylic compound is added to the above solution. A basic catalyst is then added. The solution is then properly mixed to obtain a homogeneous solution containing at least the structural units of formula (NB), the structural units of formula (NC), and the structural units of formula (1) (step aII-i).

[0123] Examples of polyfunctional (meth)acrylic compounds that can be used here include the compound represented by formula (1b-m), the compound represented by formula (1c-m), and the compound represented by formula (1d-m). k, R, and X in formula (1b-m) 1 , X 1 'and X 2 The definition and specific form of are the same as in equation (1b) above. Also, k, R, and X in equation (1c-m) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific form of are the same as those in equation (1c) above. n and R in equation (1d-m) are the same as those in equation (1d) above.

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] 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 the structural units of formula (NB), formula (NC), formula (1), and formula (2) (step aII-ii).

[0128] As a basic catalyst, amine compounds and nitrogen-containing heterocyclic compounds known in the field of organic synthesis can be used as appropriate. For example, amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds can be used as catalysts. The amount of basic catalyst used can be, for example, about 10 to 60 parts by mass per 100 parts by mass of raw material polymer. Note that using an excess of basic catalyst may increase the amount of acid required for neutralization, potentially complicating the purification process.

[0129] By heating the above solution at a temperature of preferably 60-80°C for about 3-9 hours, ring-opening of the structural unit of formula (MA) and formation of the structural unit of formula (1) contained in the raw material polymer are achieved.

[0130] For example, by adding a monofunctional (meth)acrylic compound having a hydroxyl group to the reaction system during the heating process described above, ring-opening of the structural unit of formula (MA) contained in the raw material polymer and formation of the structural unit of formula (2) occur, and polymer P(I) having the structural unit represented by formula (2) is produced.

[0131] Due to steric hindrance and other factors, monofunctional (meth)acrylic compounds containing hydroxyl groups tend to react more readily with the starting polymer than polyfunctional (meth)acrylic compounds containing hydroxyl groups. Therefore, when preparing a polymer precursor having the structural unit of formula (2), it is preferable not to add the monofunctional (meth)acrylic compound containing hydroxyl groups to the reaction system from the beginning, but rather to add it to the reaction system later. Examples of monofunctional (meth)acrylic compounds having a hydroxyl group include compounds represented by the following formulas (2a-m). In equation (2a-m), X10 The definition of R is the same as that in formula (2a).

[0132] [Chemical formula]

[0133] 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, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, and the like.

[0134] When obtaining a polymer precursor containing either the structural unit represented by formula (NB), the structural unit represented by formula (NC), and either the structural unit represented by formula (1) or the structural unit represented by formula (2), after step (I), only one of step aII-i or step aII-ii may be carried out.

[0135] (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. By step aIII-i, the structural unit represented by formula (MA) contained in the polymer precursor obtained in step aII undergoes ring-opening, and the structural unit represented by formula (3) is formed, whereby a polymer P(I) containing the structural unit represented by formula (NB), the structural unit represented by formula (NC), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (3) can be produced. When a part of the structural unit represented by formula (MA) undergoes ring-opening and a part of the structural unit of formula (MA) remains without undergoing ring-opening, the polymer P(I) further contains the structural unit represented by formula (MA).

[0136] Examples of basic catalysts used in step aIII-i include amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds.

[0137] 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 60-80°C for about 0.25-6 hours, causing the structural unit of formula (MA) contained in the polymer to open its ring and generate the structural unit represented by formula (3). The basic catalyst can be the catalyst remaining in the reaction system obtained in step aII. Therefore, it is preferable to carry out step aIII-i by adding water to the reaction mixture obtained in step aII in situ without any post-treatment of the reaction mixture.

[0138] The polymer P(I) of this embodiment can be obtained by the above steps, but from the viewpoint of the effects of the present invention, the following steps may be performed as appropriate to remove unwanted components other than the desired polymer.

[0139] First, the reaction solution, which has been 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 then left to stand for at least 30 minutes to separate the organic phase from the aqueous phase, and the aqueous phase is removed. In this way, an organic solution of the polymer is obtained.

[0140] The obtained organic solution of polymer P(I) is purified using either a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the obtained organic solution of polymer P(I) is added to an excess amount of toluene or water to reprecipitation the polymer. The polymer powder obtained by reprecipitation is then washed several more times with toluene or water. Furthermore, in order to remove formic acid and basic catalysts, the obtained polymer powder is washed with deionized water several times (approximately 1 to 3 times). High-purity polymers can be obtained by drying the polymer powder, after washing it with deionized water, at a temperature of, for example, 30-60°C for 16 hours or more. In the liquid-liquid extraction method, water or a water / methanol mixed solvent is added to the obtained organic solution of polymer P(I), and the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This mixture is allowed to stand for at least 30 minutes to separate the organic phase from the aqueous phase, and the aqueous phase is removed. Further, water or water / methanol is added to the organic solution of the polymer after the aqueous phase has been removed, and the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This mixture is allowed to stand for at least 30 minutes to separate the organic phase from the aqueous phase, and the aqueous phase is removed. In this way, an organic solution of the polymer is obtained. If necessary, the steps of adding water or water / methanol and removing the aqueous phase may be performed again. When water is used as the extraction solvent in liquid-liquid extraction, there is a tendency for the residual amounts of polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds to be higher, while when water / methanol is used, there is a tendency for the residual amounts of polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds to be lower. The obtained organic solution of polymer P(I) can be concentrated by heating under reduced pressure using a rotary evaporator, and then diluted by repeating the process of adding a final solvent (such as PGMEA) to obtain a polymer solution dissolved in the final solvent. In addition, further purification by reprecipitation after solvent replacement may be performed.

[0141] Furthermore, the polymer solution may contain the polyfunctional (meth)acrylic compound and / or monofunctional (meth)acrylic compound used in the synthesis of polymer P(I). When the polymer solution contains these (meth)acrylic compounds, it is preferable that the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart is 3 to 50%, particularly 5 to 48%, of the peak area of ​​polymer P, and the peak area derived from the monofunctional (meth)acrylic compound is 1 to 50%, particularly 2 to 35%, of the peak area of ​​polymer P. As a result, the photosensitive resin composition containing this polymer solution has good alkali solubility and good sensitivity in photolithography.

[0142] (Step aIII-ii) In step aIII-ii, the polymer obtained in step aII (polymer precursor (a)) or the polymer obtained in step aIII-i (polymer precursor (b)) is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst. By the reaction of the carboxyl groups of polymer precursor (a) or (b) with the epoxy groups of the epoxy group-containing (meth)acrylic compound, structural units represented by formula (1-1) are formed, and polymer P(I) can be produced containing structural units represented by formula (NB), structural units represented by formula (NC), structural units represented by formula (1) and / or structural units represented by formula (2), and structural units represented by formula (1-1). If a portion of the structural unit represented by formula (MA) opens its ring and a portion of the structural unit of formula (MA) remains ring-opened, polymer P(I) further contains structural units represented by formula (MA).

[0143] Step aIII-ii is preferably carried out by adding an epoxy group-containing (meth)acrylic compound to the reaction system containing the polymer precursor (b) obtained in step aIII-i.

[0144] 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 can be the same catalyst remaining in the reaction system obtained in step aII. Therefore, it is preferable to carry out step aIII-ii by adding the epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor obtained in step aII in situ, 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.

[0145] 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 60-80°C, for about 1-9 hours. This reaction between the carboxyl groups of the polymer precursor and the epoxy groups of the epoxy group-containing (meth)acrylic compound forms a structural unit represented by formula (1-1), generating polymer P(I).

[0146] Examples of epoxy group-containing (meth)acrylic compounds include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexyl methyl acrylate, 3,4-epoxycyclohexyl methyl methacrylate, and glycidyl acrylate, and one or more of these can be used.

[0147] The amount of epoxy group-containing (meth)acrylic compound added is preferably 0.1 to 3.0 moles per mole of carboxyl groups in the polymer precursor.

[0148] If polymer P(I) is a polymer obtained via polymer precursor (a), polymer P(I) includes structural units represented by formula (NB), formula (NC), formula (8), formula (9), formula (1), formula (2), and formula (MA).

[0149] If polymer P is a polymer obtained via polymer precursor (b), polymer P includes structural units represented by formula (NB), formula (NC), formula (8), formula (9), formula (5), formula (6), formula (1), formula (2), formula (3), and formula (MA).

[0150] After step aIII-ii, it is preferable to appropriately perform the following steps for removing unnecessary components other than the desired polymer P(I).

[0151] First, the reaction solution diluted with an organic solvent and added with an acid (e.g., formic acid, citric acid, etc.) above is vigorously stirred in a separatory funnel for at least 3 minutes. This is allowed to stand for 30 minutes or more to separate into an organic phase and an aqueous phase, and the aqueous phase is removed. Thus, an organic solution of polymer P(I) is obtained.

[0152] An excess amount of toluene is added to the obtained organic solution of polymer P(I) to reprecipitate polymer P(I). Further, the polymer powder obtained by reprecipitation is washed with toluene several times (e.g., 2 times). Furthermore, for removing an acid or a basic catalyst, the operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (e.g., 3 times). By drying the polymer powder after washing with ion-exchanged water at, for example, 30 to 60 °C for 16 hours or more, high-purity polymer P(I) of the present embodiment can be obtained.

[0153] (Second Embodiment) The polymer in the second embodiment of the present invention (referred to as "polymer P(II)" in this specification) includes a structural unit represented by (NB), a structural unit represented by formula (NC), a structural unit represented by formula (1-2), and at least one structural unit selected from the structural unit represented by formula (1-3), and has a structure represented by formula (P). In polymer P(II), in formula (P), a polymer chain typically composed of structural unit A, structural unit B, and structural unit C is bonded to a monofunctional or polyfunctional thiol group-containing compound-derived C1-C30 1-6-valent organic group represented as "Y". The C1-C30 1-6-valent organic group derived from this monofunctional or polyfunctional thiol group-containing compound is typically a C1-C30 organic group containing 1 to 6 thioether groups.

[0154] [Chemical formula]

[0155] In equation (P), n is an integer between 1 and 6. p, q, and r represent the molar content of structural units A, B, and C contained in each of the n polymer chains within the brackets. p, q, and r may be the same or different for each of the n polymer chains within 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 content of each structural unit A, B, and C contained in the polymer is given by p t , q t , and r t Therefore, p t +q t +r t = 1, p t It is greater than 0, preferably 0.1 to 0.6, more preferably 0.2 to 0.5, and more preferably 0.25 to 0.45. q t It 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 It is greater than 0, preferably 0.05 to 0.3, more preferably 0.06 to 0.28, and particularly preferably 0.07 to 0.25. p, q, or r may be the same or different for each of the n structural units within the brackets [ ]. X is either hydrogen or an organic group with 1 to 30 carbon atoms. Y is a 1-30 carbon atom, 1-6 valent organic group derived from monofunctional or bifunctional or multi-functional thiol group-containing compounds. A is a structural unit represented by formula (NB). B includes at least one structural unit selected from the structural units represented by formula (1-2) and the structural units represented by formula (1-3). C represents a structural unit expressed by formula (NC). Multiple instances of A, B, or C may be identical or different. D is any structure different from the structure in [ ]n, for example, one or two of A, B, and C mentioned above.

[0156] The polymer P(II) represented by formula (P) may include the structural unit represented by formula (1-1) above as structural unit B. The polymer P(II) represented by formula (P) may include the structural unit represented by formula (1-4) above as structural unit B. The polymer P(II) represented by formula (P) may include, as 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 formula (P) may include the structural unit represented by formula (3) above as structural unit B. The polymer P(II) represented by formula (P) may include, as 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 formula (P) may include the structural unit represented by formula (5) above as structural unit B. The polymer P(II) represented by formula (P) may include the structural unit represented by formula (6) above as structural unit B. The polymer P(II) represented by formula (P) may include the structural unit represented by formula (MA) as structural unit B.

[0157] In formula (P), Y is a C1-C30 1-6 valent organic group (i) derived from a monofunctional or bifunctional or more thiol group-containing compound (hereinafter referred to as "organic group (i)"). In this embodiment, the valency is the number of functional groups (number of thiol groups). That is, a monofunctional or bifunctional or more thiol group-containing compound contains one or more thiol groups, and organic group (i) is bonded to the structural units in [ ]n and [ ]m via 1-6 thioether groups derived from the thiol group. Organic group (i) may also have thiol groups that are not involved in bonding to the structural units in [ ]n and [ ]m, and polymer P(I) can be obtained as a mixture of resins with 1-6 (n+m) units (number of bonds). The organic group (i) having 1 to 30 carbon atoms is monofunctional or bifunctional or more, preferably bifunctional or more, and more preferably trifunctional or more. The upper limit is not particularly limited, but is 6-functional or less. From the viewpoint of the effects of the present invention, the valency of the organic group (i) having 1 to 30 carbon atoms is, for example, 1 to 6 valencies, preferably 2 to 6 valencies, and more preferably 3 to 6 valencies.

[0158] The 1-30 carbon-16 valent organic group (i) may contain one or more atoms selected from O, N, S, P, and Si. Examples of the 1-30 carbon-16 valent organic group (i) include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalil groups, cycloalkyl groups, alkoxy groups, and heterocyclic groups having 1-6 thioether groups (-S-* (* is a bond)).

[0159] 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.

[0160] An example of an alkynyl group is the ethynyl group. Examples of alkylidene groups include methylidene and ethylidene. Examples of aryl groups include tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups. Examples of aralkyl groups include the benzyl group and the phenethyl group. Examples of alkalyl groups include tolyl groups and xylyl groups.

[0161] Examples of cycloalkyl groups include 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 heterocyclic groups include epoxy groups and oxetanyl groups.

[0162] Examples of monofunctional or bifunctional or multi-functional thiol group-containing compounds that can derive Y in formula (P2) include compounds represented by the following chemical formulas (s-1) to (s-21). That is, polymer P(IV) contains a C1 to C30 1 to 6-valent organic group (i) derived from monofunctional or bifunctional or multi-functional thiol group-containing compounds as shown below.

[0163] [ka]

[0164] [ka]

[0165] [ka]

[0166]

change

[0167]

change

[0168]

change

[0169]

change

[0170]

change

[0171]

change

[0172]

change

[0173]

change

[0174]

change

[0175]

change

[0176]

change

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] Monofunctional or bifunctional thiol group-containing compounds may be used individually or in combination of two or more. In particular, thiol group-containing compounds with 3 to 6 thiol groups in a single molecule, which are 3 to 6 functional (3 to 6 valent), are preferred because they exhibit superior reactivity with other monomers. In this embodiment, the monofunctional or bifunctional or more thiol group-containing compound more preferably includes compounds represented by chemical formulas (s-1) to (s-3), (s-5), and (s-8) to (s-10) among the compounds represented by chemical formulas (s-1) to (s-21), and more preferably includes compounds represented by chemical formulas (s-1) to (s-3), (s-5), and (s-9). The 1-6 valent organic group (i) having 1-30 carbon atoms has a thioether group (-S-* (* is a bond)) derived from the thiol group of these thiol-containing compounds at its terminus, and bonds to the structural units in [ ]n and [ ]m via the thioether group. The organic group (i) may also have a thiol group that does not participate in bonding to the structural units in [ ]n and [ ]m.

[0185] When the polymer P(IV) of this embodiment uses a tetrafunctional (tetravalent) thiol group-containing compound represented by the above formula (s-2) as a monofunctional or bifunctional or more thiol group-containing compound, it can have a structure such as that represented by the following formula (I).

[0186] [ka]

[0187] In formula (I), A, B, C, X, p, q, and r are equivalent to those in formula (P2). However, for illustrative purposes in formula (I), p, q, and r for each polymer chain within the four brackets are represented as p 1 ~p 4 , q 1 ~q 4 , r 1 ~r 4 It should be written as follows. In equation (I), p 1 ~p 4 , q 1 ~q 4 , r 1 ~r 4 The polymer chains within the four brackets may be the same or different, and p 1 +q 1 +r1 =1, p 2 +q 2 +r 2 =1, p 3 +q 3 +r 3 =1, p 4 +q 4 +r 4 = 1 The molar content of each structural unit A, B, and C in the polymer represented by formula (I) is given by p t , q t , and r t Therefore, p t =p 1 +p 2 +p 3 +p 4 , q t =q 1 +q 2 +q 3 +q 4 , r t =r 1 +r 2 +r 3 +r 4 That is the case.

[0188] In formula (I), the bonding order of A, B, and C is not particularly limited, and any of A, B, or C may be bonded to the thioether group. Furthermore, although formula (I) is shown as an example in which the four structural units in [ ] are bonded via thioether groups derived from the four mercapto groups of the compound represented by chemical formula (s-2), it is also possible that 1 to 3 structural units in [ ] are bonded to the thioether groups derived from the four mercapto groups, and the remaining thioether groups are bonded to organic groups different from the structural units in [ ]. In this embodiment, polymer P can be obtained as a mixture containing at least one compound in which 1 to 4 of the structures in [ ] are bonded.

[0189] The physical properties of polymer P(II), such as weight-average molecular weight Mw, dispersion (weight-average molecular weight Mw / number-average molecular weight Mn), glass transition temperature, softening point, melting point, acid value, double bond equivalent, and alkali dissolution rate, are the same as those of polymer P(I) described above.

[0190] (Method for manufacturing polymer P(II)) Polymer P(II) can be produced (synthesized) by any method. Typically, polymer P(II) can be produced by the following steps bI, bII, and bIII. Step bI: A step of preparing a raw material polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (NC), a structural unit represented by formula (MA), and a 1-6 valent organic group (i) having 1-30 carbon atoms; Step bII: This step involves reacting the raw material polymer obtained in Step bI with a compound having a hydroxyl group and two or more (meth)acryloyl groups (a polyfunctional (meth)acrylic compound), and / or a compound having a hydroxyl group and one (meth)acryloyl group (a monofunctional (meth)acrylic compound), in the presence of a basic catalyst, to prepare polymer P(II) which contains a structural unit represented by formula (NB), a structural unit represented by formula (NC), a C1-C30 1-6 valent organic group (i), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further containing a structural unit represented by formula (MA).

[0191] If polymer P(II) further contains structural units represented by formula (3), the following step bIII-i is performed. Step bIII-i: A polymer precursor (corresponding to polymer P(II) in step bII) is prepared in step bII, comprising a structural unit represented by formula (NB), a structural unit represented by formula (NC), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), a 1-6 valent organic group (i) having 1-30 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).

[0192] If polymer P(II) further contains structural units represented by formula (1-1), the following step bIII-ii is performed. Step bIII-ii: A polymer precursor (corresponding to polymer P(I) in step bII) obtained in step bII, comprising a structural unit represented by formula (NB), a structural unit represented by formula (NC), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), a 1-6 valent organic group (i) having 1-30 carbon atoms, and optionally a further structural unit represented by formula (MA), and a polymer precursor being reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare polymer P(II).

[0193] Either step bIII-i or step bIII-ii may be performed. If both are performed, it is preferable to perform step bIII-ii after step bIII-i.

[0194] In step bII, when both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used, it is preferable to first react the polyfunctional (meth)acrylic compound with the raw material polymer obtained in step bI, and then react the resulting reaction mixture with the monofunctional (meth)acrylic compound.

[0195] The following describes each step. (Process bI) The step in step bI, which involves preparing a raw material polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (NC), a structural unit represented by formula (MA), and a 1-6 valent organic group (i) having 1 to 30 carbon atoms, can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (NBm), a monomer represented by formula (NCm), and a monomer represented by formula (MAm) in the presence of a monofunctional or bifunctional or more thiol group-containing compound.

[0196] Examples of monofunctional or bifunctional thiol group-containing compounds include, but are not limited to, the compounds represented by the chemical formulas (s-1) to (s-21) above. Monofunctional or bifunctional thiol group-containing compounds may be used individually or in combination of two or more. The specific conditions for step bI are the same as those for step aI in the method for producing polymer P(I) of the first embodiment.

[0197] (Step bII) Step bII can be performed under the same conditions as step aII in the method for producing polymer P(I) of the first embodiment.

[0198] (Step bIII-i) Step bIII-i can be performed under the same conditions as step aIII in the method for producing polymer P(I) of the first embodiment. (Step bIII-i) Step bIII-ii can be performed under the same conditions as step aIII in the method for producing polymer P(I) of the first embodiment.

[0199] (Third embodiment) The polymer in the third embodiment of the present invention (hereinafter referred to as "polymer P(III)") is prepared by polymerizing a monomer composition comprising a monomer represented by the following formula (NBm), a monomer represented by the following formula (NCm), and a monomer represented by the following formula (MAm) in the presence of a monofunctional or bifunctional or more thiol group-containing compound to prepare a raw material polymer (step bI). This polymer is obtained by reacting the raw material polymer with a compound having a hydroxyl group and two or more (meth)acryloyl groups, and / or a compound having a hydroxyl group and one (meth)acryloyl group, in the presence of a basic catalyst (step bII).

[0200] [ka]

[0201] In the formula (NBm), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2.

[0202] [ka]

[0203] In the formula (NCm), R 11 , R 12 , R 13 and R 14 At least one of them is a -Z-COOH group, where Z is a single bond, -CH2-, or -(CH2)2-, and the other R is 11 , R 12 , R 13 and R 14 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and a 11 It is 0, 1, or 2.

[0204] [ka]

[0205] In the formula (MAm), R 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0206] Polymer P(III) has a structure in which a side chain derived from a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as a "polyfunctional (meth)acrylic compound") and / or a compound having a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as a "monofunctional (meth)acrylic compound") used in step bII above is introduced into a raw material polymer composed of structural units derived from the raw material monomers used in step bI above (i.e., structural units derived from monofunctional or bifunctional or more thiol group-containing compounds, structural units derived from norbornene monomer represented by formula (NBm), structural units derived from norbornene carboxylic acid represented by formula (NCm), and structural units derived from maleic anhydride monomer represented by formula (MAm)). Here, the side chain derived from the polyfunctional / monofunctional (meth)acrylic compound is a residue obtained by removing a hydrogen atom from the hydroxyl group of the polyfunctional / monofunctional (meth)acrylic compound, and is a group having at least one (meth)acryloyl group.

[0207] The physical properties of polymer P(III), such as weight-average molecular weight Mw, dispersion (weight-average molecular weight Mw / number-average molecular weight Mn), glass transition temperature, softening point, melting point, acid value, double bond equivalent, and alkali dissolution rate, are the same as those of polymer P(I) described above.

[0208] The polymer P(III) of this embodiment contains a thioether group derived from a monofunctional or bifunctional or more thiol group-containing compound in its structure. Due to the presence of the thioether group, polymer P(III) exhibits excellent sensitivity in photolithography and higher alkali solubility, thus providing a resin cured product with superior developability. Furthermore, the inclusion of the thioether group in polymer P(III) reduces yellowing and provides a resin cured product with excellent transparency.

[0209] Furthermore, P(III) in this embodiment has a structural unit derived from norbornene represented by formula (NBm). The structural unit derived from norbornene monomer is chemically robust. Therefore, polymer P(II) containing this structural unit exhibits little weight loss and is stable when subjected to heat treatment.

[0210] Furthermore, the polymer P(III) of this embodiment has structural units derived from norbornenecarboxylic acid represented by formula (NCm). By introducing structural units derived from norbornenecarboxylic acid into polymer P(III), the balance between sensitivity, alkali solubility, and heat discoloration resistance is improved to a high level. Therefore, photosensitive resin compositions containing polymer P(III) can be suitably used to manufacture films and filters for use in liquid crystal display devices and solid-state image sensors where sensitivity and heat yellowing resistance are required.

[0211] Furthermore, polymer P(III) of this embodiment has an organic group containing a (meth)acryloyl group in its side chain. Polymer P(III) may be, for example, a resin having a thioether group and a monofunctional (meth)acryloyl group, a resin having a thioether group and a polyfunctional (meth)acryloyl group, or a resin having a thioether group, a monofunctional (meth)acryloyl group, and a polyfunctional (meth)acryloyl group. Polymer P(III) has excellent sensitivity because the curing reaction (polymerization reaction) is accelerated by the presence of the (meth)acryloyl group.

[0212] (Fourth embodiment) The polymer in the fourth embodiment of the present invention (hereinafter referred to as "polymer P(IV)") is prepared by polymerizing a monomer composition containing the monomer represented by formula (NBm), the monomer represented by formula (NCm), and the monomer represented by formula (MAm) in the presence of a monofunctional or bifunctional or more thiol group-containing compound (step bI), This raw material polymer is reacted with a compound having a hydroxyl group and two or more (meth)acryloyl groups, and / or a compound having a hydroxyl group and one (meth)acryloyl group, in the presence of a basic catalyst to prepare a polymer precursor (a) (step bII). This polymer is obtained by treating the polymer precursor (a) with water in the presence of a basic catalyst (step bIII-i).

[0213] In the fourth embodiment, polymer P(IV) may be a polymer obtained by reacting polymer precursor (a) with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst (step bIII-ii).

[0214] In the fourth embodiment, polymer P(IV) may be a polymer obtained by treating polymer precursor (a) with water in the presence of a basic catalyst (step bIII-i), or by reacting polymer precursor (b) with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst (step bIII-ii).

[0215] The physical properties of polymer P(IV), such as weight-average molecular weight Mw, dispersion (weight-average molecular weight Mw / number-average molecular weight Mn), glass transition temperature, softening point, melting point, acid value, double bond equivalent, and alkali dissolution rate, are the same as those of polymer P(I) described above.

[0216] In the fourth embodiment, polymer P(IV) has, in addition to the structural units constituting polymer P(III) in the second embodiment described above, structural units derived from maleic anhydride monomer represented by formula (MAm) contained in the polymer precursor obtained in step bII, which are ring-opened with water by the treatment in step bIII (dicarboxylic acid structural units). Such polymer P(IV) may have high alkali solubility, and as a result, the photosensitive resin composition containing polymer P(IV) has excellent developability when subjected to a photolithography method using an alkaline aqueous solution as a developer.

[0217] [Polymer solution] The polymer solution of this embodiment comprises the polymer P(I), polymer P(II), polymer P(III), or P(IV) described above. The polymer solution of this embodiment may also contain, along with polymer P(I), polymer P(II), polymer P(III), or P(IV), at least one selected from polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds.

[0218] (Polyfunctional (meth)acrylic compounds) The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that may be contained in the polymer solution of this embodiment may be unreacted (meth)acrylic compounds used in step aII or step bII of the production of polymer P, or may be added separately.

[0219] Examples of polyfunctional (meth)acrylic compounds that can be incorporated into polymer solutions include, but are not limited to, the compounds represented by the following formulas (1b-p), (1c-p), and (1d-p).

[0220] [ka]

[0221] [ka]

[0222] [ka]

[0223] k, R, X in equation (1b-p) 1 , X 1 'and X 2 The definition and specific form of are the same as in equation (1b) above. Also, k, R, and X in equation (1c-p) 1 , X2 , X 3 , X 4 , X 5 and X 6 The definition and specific form of are the same as those in formula (1c) above.

[0224] In formulas (1b-p), (1c-p), and (1d-p), Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0225] Compounds in formulas (1b-p), (1c-p), and (1d-p) where Y is a hydrogen atom may be unreacted monomers (i.e., compounds represented by formulas (1b-p), (1c-p), and (1d-p)) and may be added separately. In equation (1d-p), n is an integer greater than or equal to 2, preferably an integer between 2 and 5, and more preferably an integer between 2 and 3.

[0226] When a polyfunctional (meth)acrylic compound is added to the polymer solution of this embodiment separately from the unreacted polyfunctional (meth)acrylic compound used in the production of polymer P(I), polymer P(II), polymer P(III), or P(IV), the amount added may be such that the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less, relative to the peak area of ​​polymer P(I), polymer P(II), polymer P(III), or P(IV).

[0227] (Monofunctional (meth)acrylic compounds) Examples of monofunctional (meth)acrylic compounds incorporated into the polymer solution of this embodiment include compounds represented by the following formula (2a-m). In formula (2a-m), X 10 The definition of R is the same as that in equation (2a).

[0228] [ka]

[0229] When a monofunctional (meth)acrylic compound is added to the polymer solution of this embodiment separately from the unreacted monofunctional (meth)acrylic compound used in the production of polymer P(I), polymer P(II), polymer P(III), or P(IV), the amount added may be such that the peak area derived from the monofunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less, relative to the peak area of ​​polymer P(I), polymer P(II), polymer P(III), or P(IV).

[0230] The polymer solution of this embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. As the organic solvent, one or more of the following can be used: ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, etc.

[0231] Specific examples of organic solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyl lactone, N-methylpyrrolidone, and cyclohexanone. These may be used individually or in combination of two or more. The amount of organic solvent used is not particularly limited, but it is used in such an amount that the concentration of nonvolatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0232] [Production of polymer solutions] The polymer solution of this embodiment can be prepared by mixing the above components by a known method. The polymer solution of this embodiment is used as a resin material in the photosensitive resin composition described below.

[0233] [Photosensitive resin composition] The photosensitive resin composition of this embodiment comprises the above-mentioned polymer P(I), polymer P(II), polymer P(III), or polymer P(IV), and a photopolymerization initiator. That is, the photosensitive resin composition of this embodiment comprises the polymer solution of this embodiment described above and a photopolymerization initiator. Each component is described below.

[0234] (Photopolymerization initiator) Examples of photopolymerization initiators used in the photosensitive resin composition of this embodiment include photoradical polymerization initiators. Known compounds can be used as photoradical polymerization initiators, such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1 Alkylphenone compounds such as -one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone; benzoin methyl ether, benzoin ethyl Benzoin compounds such as benzoin ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxynaphthyl)- Halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbokynylnaphthyl)-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)], etanone, Examples include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-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. The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, per 100 parts by mass of polymer P.

[0235] The photosensitive resin composition of this embodiment, by containing the above-mentioned components, has high sensitivity in photolithography processing and excellent alkali solubility. Therefore, the photosensitive resin composition has excellent developability and excellent processability in the photolithography method.

[0236] (Coloring agent) In one embodiment, the photosensitive resin composition may contain a coloring agent. The inclusion of a coloring agent makes it suitable for use as a material for forming color filters in liquid crystal displays and solid-state image sensors. Various pigments or dyes can be used as the coloring agent. Organic pigments and inorganic pigments can be used as pigments.

[0237] 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, pyromethene pigments, and dye lake pigments.

[0238] Inorganic pigments that can be used include white and extender pigments (titanium dioxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (lead yellow, cadmium-based pigments, chrome vermilion, nickel titanium, chromium titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), luminescent pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

[0239] As dyes, for example, known dyes described in Japanese Patent Publication No. 2003-270428, Japanese Patent Publication No. Hei 9-171108, Japanese Patent Publication No. 2008-50599, etc., can be used. If the photosensitive resin composition contains a coloring agent, the photosensitive resin composition may contain only one type of coloring agent or two or more types.

[0240] Colorants (especially pigments) can be of an appropriate average particle size depending on the purpose and application. In particular, when transparency is required, such as in color filters, a small average particle size of 0.1 μm or less is preferred, while in other cases, such as in paints where opacity is required, a larger average particle size of 0.5 μm or more is preferred.

[0241] Depending on the purpose and application, the colorants may undergo surface treatments such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, or wax coating.

[0242] If the photosensitive resin composition contains a colorant, the amount can be set appropriately depending on the purpose and application, but in order to balance the color concentration and the dispersion stability of the colorant, it is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass, relative to the total nonvolatile components (components excluding solvents) of the photosensitive resin composition.

[0243] (Surfactants) The photosensitive resin composition of this embodiment may contain a surfactant, and a nonionic surfactant is preferred as the surfactant.

[0244] The inclusion of a nonionic surfactant improves the coatability of the photosensitive resin composition when applying it to a substrate to obtain a resin film, allowing for the creation of a coating film of uniform thickness. Furthermore, it prevents residue and pattern lifting during the development of the coating film.

[0245] Nonionic surfactants are, for example, compounds containing a fluorine group (e.g., a fluorinated alkyl group) or a silanol group, or compounds with a siloxane bond as the main skeleton. In this embodiment, it is more preferable to use a nonionic surfactant that includes 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 from DIC Corporation, and Novec FC4430 and FC4432 from Sumitomo 3M Co., Ltd. When using a surfactant, the amount of surfactant added is preferably 0.01 to 10% by weight per 100 parts by weight of resin.

[0246] (solvent) Photosensitive resin compositions typically contain a solvent. Organic solvents are preferred as the solvent. Specifically, one or more of the following can be used: ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, etc.

[0247] Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutylcarbinol (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 solvent used is not particularly limited, but it is used in such an amount that the concentration of nonvolatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0248] (Light-blocking agent) The resin composition of this embodiment may contain a light-shielding agent. The photosensitive resin composition may contain only one type of light-shielding agent, or it may contain two or more types.

[0249] When a photosensitive resin composition contains a light-shielding agent, the amount can be set appropriately depending on the purpose and application, but in order to balance light-shielding performance and dispersion stability of the light-shielding agent, the amount is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass, relative to the total non-volatile components (components excluding solvents) of the photosensitive resin composition.

[0250] (Crosslinking agent) The photosensitive resin composition of this embodiment may contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it is capable of crosslinking polymer P (i.e., chemically bonding with polymer P) through the action of activated chemical species generated from the photopolymerization initiator. The crosslinking agent may not only chemically bond with the polymer, but may also react with other crosslinking agents to form bonds.

[0251] The crosslinking agent is preferably a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule (however, the crosslinking agent does not fall under the polymers mentioned above). Using a crosslinking agent having the same type of crosslinkable group (polymerizable double bond) as the polymer is preferable in terms of uniform curability and further improvement of sensitivity. There is no particular upper limit to the number of functionalities (number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, preferably 6 or less.

[0252] Specifically, the 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 oxide-added ditrimethylolpropanetetra(meth)acrylate, ethylene oxide-added pentaerythritoltetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropanetri(meth)acrylate, propylene oxide-added ditrimethylolpropanetetra(meth)acrylate, propylene oxide-added pentaerythritoltetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropanetri(meth)acrylate, ε-caprolactone-added ditrimethylolpropanetetra(meth)acrylate, ε-caprolactone-added pentaerythritoltetra(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 hexanyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexanyl ether; Vinyl ether group-containing (meth)acrylic acid esters such as (meth)acrylate 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 2-(vinyloxyethoxyethoxyethoxy)ethyl; 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 (meth)acrylic acid allyl; 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 the reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; Examples include:

[0253] Among 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.

[0254] When a photosensitive resin composition contains a crosslinking agent, the composition may contain only one type of crosslinking agent or two or more types. When a photosensitive resin composition contains a crosslinking agent, the amount can be appropriately set according to the purpose and application. As an example, the amount of crosslinking agent can usually be about 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, per 100 parts by mass of photosensitive resin.

[0255] (Other additives) Depending on the purpose and required properties, the photosensitive resin composition may also contain components such as fillers, binder resins other than the polymers mentioned above, acid generators, heat resistance improvers, developing aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, matting agents, defoamers, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, oscillating agents, oscillating aids, silane coupling agents, and polyvalent phenol compounds.

[0256] [Application] A patterned film can be obtained by forming a film using the above-described photosensitive resin composition and then exposing and developing the film to form a pattern. This film can be applied to color filters, black matrices, and the like. In other words, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a coloring agent. A black matrix can also be obtained by forming a pattern using a photosensitive resin composition containing a light-shielding agent. Then, liquid crystal display devices and solid-state image sensors equipped with color filters and black matrices can be manufactured. This section describes a typical procedure for forming a pattern.

[0257] (Formation of a photosensitive resin film) For example, the above photosensitive resin composition is applied to any substrate and dried as necessary to first obtain a photosensitive resin film.

[0258] The substrate to which the composition is applied is not particularly limited. Examples 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 with electrodes or elements formed on its surface. It may also be surface-treated to improve adhesion.

[0259] The method of coating the photosensitive resin composition is not particularly limited. It can be done by rotary coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, inkjet method, etc.

[0260] The photosensitive resin composition applied to the substrate is typically dried by heat treatment using a hot plate, hot air, oven, etc. The heating temperature is usually 80 to 140°C, preferably 90 to 120°C. The heating time is usually 30 to 600 seconds, preferably 30 to 300 seconds.

[0261] The thickness of the photosensitive resin film is not particularly limited and can be adjusted as appropriate depending on the pattern to be ultimately obtained, but is usually 0.5 to 10 μm, preferably 1 to 5 μm. The film thickness can be adjusted by the solvent content in the photosensitive resin composition and the application method.

[0262] (exposure) Exposure is typically performed by irradiating a photosensitive resin film with active light through a suitable photomask.

[0263] Examples of active light include X-rays, electron beams, ultraviolet light, and visible light. In terms of wavelength, light in the range of 200 to 500 nm is preferred. In terms of pattern resolution and handling ease, the light source is preferably the g-line, h-line, or i-line of a mercury lamp, with the i-line being particularly preferred. Alternatively, two or more light rays may be mixed and used. As the exposure apparatus, a contact aligner, mirror projection, or stepper is preferred. The amount of light used for exposure can be adjusted as appropriate depending on the amount of photosensitive agent in the photosensitive resin film, for example, 100-500 mJ / cm². 2 It is to that extent.

[0264] Furthermore, if necessary, the photosensitive resin film may be heated again after exposure (post-exposure baking). The temperature is, for example, 70 to 150°C, preferably 90 to 120°C. The time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. Post-exposure baking promotes the reaction by radicals generated from the photoradical polymerization initiator, further accelerating the curing reaction.

[0265] (developing) A pattern can be obtained by developing an exposed photosensitive resin film with a suitable developer, and a substrate with the pattern can be manufactured. The photosensitive resin film made from the photosensitive resin composition containing the polymer solution of this embodiment exhibits excellent adhesion to the substrate, thereby suppressing pattern peeling during the development process.

[0266] In the development process, development can be carried out using a suitable developer solution and methods such as immersion, paddle, or rotary spray. Development removes the exposed areas (in the case of positive film) or unexposed areas (in the case of negative film) of the photosensitive resin film, thereby obtaining a pattern. The type of developer that can be used is not particularly limited. For example, alkaline aqueous solutions and organic solvents can be used.

[0267] Examples of specific alkaline aqueous solutions include (i) inorganic alkaline aqueous solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) organic amine aqueous solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine; and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. The polymer of this embodiment has adjusted alkali solubility and excellent sensitivity, so when using a strongly basic developer such as TMAH (tetramethylammonium hydroxide) solution, the pattern after exposure and development can be made into the shape as designed.

[0268] Examples of organic solvents include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether solvents such as propylene glycol monomethyl ether. The developing solution may contain, for example, water-soluble organic solvents such as methanol or ethanol, or surfactants.

[0269] In this embodiment, it is preferable to use an alkaline aqueous solution as the developer, and more preferable to use tetramethylammonium hydroxide, an aqueous sodium carbonate solution, or an aqueous potassium hydroxide solution. The concentration of the alkaline aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.5 to 5% by mass. Through the above process, a pattern can be obtained and a substrate with the pattern can be manufactured, but various processing steps may be performed after development.

[0270] For example, after development, the pattern and substrate may be washed with a rinsing solution. Examples of rinsing solutions include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These may be used individually or in combination of two or more.

[0271] The resulting pattern may also be heated to ensure sufficient curing. The heating temperature is typically 150-400°C, preferably 160-300°C, and more preferably 200-250°C. The heating time is not particularly limited, but is, for example, in the range of 15-300 minutes. This heat treatment can be carried out using a hot plate, an oven, or a heating oven with a temperature programmable. The atmospheric gas used during the heat treatment may be air, or an inert gas such as nitrogen or argon. Heating may also be carried out under reduced pressure. Figure 1 schematically shows an example of the structure of a liquid crystal display device and / or solid-state image sensor that includes a color filter and / or black matrix. While the black matrix may be replaced with a black bank, the following description focuses on liquid crystal display devices and / or solid-state image sensors that include both a color filter and a black matrix.

[0272] A black matrix 11 and a color filter 12 are formed on the substrate 10. A protective film 13 and a transparent electrode layer 14 are provided above the black matrix 11 and color filter 12.

[0273] The substrate 10 is typically made of a light-transmitting material, such as glass, polyester, polycarbonate, polyolefin, polysulfone, or polymers of cyclic olefins. The substrate 10 may also be subjected to corona discharge treatment, ozone treatment, chemical treatment, etc., as needed. The substrate 10 is preferably made of glass. The black matrix 11 is composed, for example, of a cured product of a photosensitive resin composition containing a light-shielding agent.

[0274] Typically, there are three colors for the color filter 12: red, green, and blue. The color filter 12 is composed of a cured product of a photosensitive resin composition containing a coloring agent corresponding to each color.

[0275] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. Further embodiments of the present invention are described below. [1] A process of preparing a raw material polymer by polymerizing a monomer composition comprising a monomer represented by the following formula (NBm), a monomer represented by the following formula (NCm), and a monomer represented by the following formula (MAm) in the presence of a monofunctional or bifunctional or more thiol group-containing compound, A method for producing a polymer, comprising the step of reacting the raw material polymer with a compound having a hydroxyl group and two or more (meth)acryloyl groups, and / or a compound having a hydroxyl group and one (meth)acryloyl group, in the presence of a basic catalyst, to obtain a polymer, [ka] In the formula (NBm), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2. [ka] In the formula (NCm), R 11 , R 12 , R 13 and R 13 At least one of them is a -Z-COOH group, where Z is a single bond, -CH2-, or -(CH2)2-, and the other R is 11 , R 12 , R 13 and R 13 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and a 11 is 0, 1, or 2, [ka] In the formula (MAm), R 21 and R 22A method for producing polymers, wherein each is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. [2] A process of preparing a raw material polymer by polymerizing a monomer composition comprising a monomer represented by the following formula (NBm), a monomer represented by the following formula (NCm), and a monomer represented by the following formula (MAm) in the presence of a monofunctional or bifunctional or more thiol group-containing compound, The process involves reacting the aforementioned raw material polymer with a compound having a hydroxyl group and two or more (meth)acryloyl groups, and / or a compound having a hydroxyl group and one (meth)acryloyl group, in the presence of a basic catalyst, to prepare a polymer precursor. A method for producing a polymer, comprising the step of obtaining a polymer by treating the polymer precursor with water in the presence of a basic catalyst, [ka] In the formula (NBm), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2. [ka] In the formula (NCm), R 11 , R 12 , R 13 and R 13 At least one of them is a -Z-COOH group, where Z is a single bond, -CH2-, or -(CH2)2-, and the other R is 11 , R 12 , R 13 and R 13 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and a 11 is 0, 1, or 2, [ka] In the formula (MAm), R 21 and R 22A method for producing polymers, wherein each is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. [3] A method for producing a polymer according to [1] or [2], wherein the monofunctional or monofunctional or bifunctional or more thiol group-containing compound is at least one compound selected from formulas (s-1) to (s-21). [ka] A method for producing a polymer according to any one of [1] to [3], A method for producing a polymer, wherein the weight-average molecular weight of the polymer is 3,000 or more and 15,000 or less. A polymer solution comprising a polymer obtained by any of the polymer manufacturing methods described in [5] [1] to [4]. [6] [5] The polymer solution described above, A polymer solution further comprising a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof. A polymer solution as described in [7] [5] or [6], A polymer solution used to form a color filter or black matrix. A polymer obtained by a polymer manufacturing method described in any of [8] [1] to [4], A photosensitive resin composition comprising a photoradical polymerization initiator. [Examples]

[0276] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0277] The compounds used in the examples may be indicated by the following abbreviations or trade names. MAN: Maleic anhydride NB:2-Norbornen NC:5-norbornene-2-carboxylic acid ·ST: Styrene • PhMI:N-phenylmaleimide • 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 Chemicals Co., Ltd.) 4-HBA: 4-hydroxybutyl acrylate • A-TMM-3LM-N: A mixture of the following two compounds. Based on gas chromatography measurements, the amount of the compound on the left in the mixture is approximately 57% (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0278] [ka]

[0279] <Synthesis of raw material polymers> (Synthesis of raw material polymer 1) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 602.56 g of a 75% toluene solution of 2-norbornene (equivalent to 451.92 g of 2-norbornene, 4.8 mol), maleic anhydride (MAN, 470.69 g, 4.8 mol), and 2281.74 g of methyl ethyl ketone (MEK) were added and stirred until dissolved. Next, dissolved oxygen was removed from the system by nitrogen bubbling, and the mixture was heated. When the internal temperature reached 80°C, a solution of 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., 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 reaction was then continued at 80°C for 7 hours. Finally, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 3686.4 g of methanol to precipitate a white solid. The obtained white solid was then washed with another 3686.4 g of methanol and vacuum-dried at 120°C to obtain 910.1 g of a polymer (raw material polymer 1) comprising structural units derived from 2-norbornene and structural units derived from maleic anhydride. The obtained raw material polymer 1 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 3500, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.62.

[0280] (Confirmation of the thioether structure contained in raw material polymer 1) The elemental PEMP is represented by the following chemical formula. 13 1C-NMR measurements revealed a peak a originating from carbon a at approximately 19.0 ppm and a peak b originating from carbon b at approximately 62.0 ppm.

[0281] [ka]

[0282] Raw material polymer 1 synthesized using PEMP 13 In 1C-NMR measurements, a peak b originating from carbon b was observed at approximately 62.0 ppm. GPC measurements of the reaction solution showed no peak for PEMP alone, indicating that no unreacted PEMP remained, thus confirming that PEMP was incorporated into the raw material polymer 1.

[0283] Also, raw material polymer 1 13 In 1C-NMR measurements, peak a, originating from carbon a, was not observed. Instead, peak c, corresponding to a thioether (RS-R'), appeared around 28 ppm. Since the integral value of peak c is approximately twice that of peak b, it was determined that the raw material polymer 1 has a skeleton containing a thioether group as described below, and the thiol group has disappeared.

[0284] [ka]

[0285] 13 The conditions for 1C-NMR measurement are as follows: (Test conditions) The measurement sample was prepared by adding the measurement solvent to the weighed sample to adjust the concentration, and then pouring the specified amount into an NMR measurement sample tube. • Measurement equipment: JEOL JNM-ECA400 superconducting FT-NMR spectrometer ·Resonance frequency: 100.53MHz • Measurement nucleus: 13 C • Measurement method: NNE measurement (inverse gate decoupling method) • Pulse width: 3.83 μsec • Pulse repetition waiting time: 30s • Total number of times: 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 elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the polymer. Furthermore, GPC analysis of the reaction solution before methanol addition showed the disappearance of the PEMP-derived peak, confirming that PEMP was incorporated into the starting polymer 1.

[0286] Elemental analysis revealed that the sulfur content in raw polymer 1 was 2.4 wt%.

[0287] (Synthesis of raw material polymer 2) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 115.49 g of a 75% toluene solution of 2-norbornene (equivalent to 86.62 g of 2-norbornene, 0.920 mol), maleic anhydride (MAN, 112.77 g, 1.150 mol), and 104.05 g of methyl ethyl ketone (MEK) were added and stirred until dissolved. Next, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated until the internal temperature reached 80°C. Then, a solution of 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.59 g, 0.046 mol), styrene 23.95 g (0.230 mol), and PEMP (22.48 g, 0.046 mol) dissolved in 102.1 g of MEK was added over 1 hour. The reaction was then continued at 80°C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 2457.3 g of methanol to precipitate a white solid. The obtained white solid was further washed with 614.3 g of methanol and then vacuum-dried at 120°C to obtain 220.0 g of a polymer (raw material polymer 2) comprising structural units derived from 2-norbornene, structural units derived from styrene, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 4,700, and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.30. Regarding raw material polymer 2, 13 The ratio of structures derived from each monomer actually introduced into the raw material polymer, as calculated by 13C-NMR, was norbornene:styrene:maleic anhydride = 40.9%:10.7%:48.4%, and the amount of PEMP actually introduced into the raw material polymer was 1.9 mol% of the total amount of each monomer.

[0288] (Confirmation of the structure of raw material polymer 2) The amounts (mole fraction, mol%) of structural units derived from PEMP, styrene (structural units of formula (ST)), maleic anhydride (structural units of formula (MA)), and norbornene (structural units of formula (NB)) in raw material polymer 2 are as follows: 13The values ​​were calculated by integral analysis of 1C-NMR. 13 The 1C-NMR chart is shown in Figure 2. 13 The chemical shifts in the 1C-NMR chart were assigned to each structural unit as follows, and the corresponding integral values ​​were measured. PEMP k(4C): 62.0~64.0 ppm • Styrene aromatic ring (6C): 126.0~134.0 ppm • Maleic anhydride ester (2C) + PEMP g(4C): 170.0~174.7 ppm • Maleic acid ester (2C) (a structure in which maleic anhydride has been opened): 174.7~178.0 ppm Alkyl chain: 20-60 ppm • DMSO: around 40 ppm Norbornene(7C) = alkyl chain - DMSO - PEMP(9C, h+i+j) - maleic anhydride(2C) - maleic acid(2C) - styrene(2C) Here, the structural ratio derived from maleic anhydride that was actually introduced into the raw material polymer was calculated by including not only the structural unit of formula (MA) but also the structure of maleic acid obtained by ring-opening maleic anhydride.

[0289] The amount of sulfur in the obtained raw material polymer 2 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in raw material polymer 2. In addition, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0290] (Synthesis of raw material polymer 3) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 144.36 g of a 75% toluene solution of 2-norbornene (equivalent to 108.27 g of 2-norbornene, 1.150 mol), 90.22 g (0.920 mol) of maleic anhydride (MAN), 39.83 g (0.230 mol) of N-phenylmaleimide, and 122.77 g of methyl ethyl ketone (MEK) were added and stirred until dissolved. Then, dissolved oxygen in the system was removed by nitrogen bubbling, and the system was heated until the internal temperature reached 80°C. Dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., product name: V-601, 10.59 g, 0.046 mol) was added. A solution of PEMP (22.48 g, 0.046 mol) dissolved in 91.11 g of MEK was added over 1 hour. The reaction was then carried out at 80°C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was precipitated as a white solid by dropping it into 2457.3 g of methanol. The obtained white solid was then washed with 614.3 g of methanol and vacuum-dried at 120°C to obtain 209.9 g of polymer (raw material polymer 3) comprising structural units derived from 2-norbornene, N-phenylmaleimide, and maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 3,700, and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.74. Regarding raw material polymer 3, 13 The ratio of structures derived from each monomer actually introduced into the raw material polymer, as calculated by 13C-NMR, was norbornene::N-phenylmaleimide:maleic anhydride = 52.0%:11.6%:36.4%, and the amount of PEMP actually introduced into the raw material polymer was 2.3 mol% of the total amount of each monomer.

[0291] The amount of sulfur in the obtained raw material polymer 3 was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in raw material polymer 3. Furthermore, GPC measurement of the reaction solution before methanol addition showed the disappearance of the peak derived from PEMP, confirming that PEMP was incorporated into the polymer. (Confirmation of the structure of raw material polymer 3) The amounts (mole fraction, mol%) of structural units derived from PEMP, N-phenylmaleimide (PhMI) (structural units of formula (MI)), maleic anhydride (structural units of formula (MA)), and norbornene (structural units of formula (NB)) in raw material polymer 3 are as follows: 13 The values ​​were calculated by integral analysis of 1C-NMR. 13 The 1C-NMR chart is shown in Figure 3. 13 The chemical shifts in the 1C-NMR chart were assigned to each structural unit as follows, and the corresponding integral values ​​were measured. PEMP k(4C): 62.0~64.0 ppm ·PhMI aromatic ring (6C): 126.0~134.0ppm • Maleic anhydride ester (2C) + PEMP g(4C): 170.0~174.7 ppm • Maleic acid ester (2C) (a structure in which maleic anhydride has been opened): 174.7~178.0 ppm Alkyl chain: 20-60 ppm • DMSO: around 40 ppm Norbornene(7C)=alkyl chain-DMSO-PEMP(9C, h+i+j)-maleic anhydride(2C)-maleic acid(2C)-PhMI(2C) Here, the structural ratio derived from maleic anhydride that was actually introduced into the raw material polymer was calculated by including not only the structural unit of formula (MA) but also the structure of maleic acid obtained by ring-opening maleic anhydride.

[0292] (Synthesis of raw material polymer 4) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 115.49 g of a 75% toluene solution of 2-norbornene (equivalent to 86.62 g of 2-norbornene, 0.920 mol), maleic anhydride (MAN, 112.77 g, 1.150 mol), 31.78 g of 5-norbornene-2-carboxylic acid (0.230 mol), and 232.48 g of methyl ethyl ketone (MEK) were added and stirred until dissolved. Next, dissolved oxygen in the system was removed by nitrogen bubbling, and the system was heated until the internal temperature reached 80°C. Then, a solution of dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.59 g, 0.046 mol) and PEMP (22.48 g, 0.046 mol) dissolved in 68.70 g of MEK was added over 1 hour. The reaction was then carried out at 80°C for a further 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 2536.4 g of methanol to precipitate a white solid. The obtained white solid was then washed with 2634.1 g of methanol and vacuum-dried at 120°C to obtain 196.2 g of polymer (raw material polymer 4) comprising structural units derived from 2-norbornene, structural units derived from 5-norbornene-2-carboxylic acid, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 3,600, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.47. 1 The acid value of raw material polymer 4, calculated by 1H-NMR measurement, was 39 mgKOH / g, confirming that a carboxyl group derived from 5-norbornene-2-carboxylic acid was introduced into raw material polymer 4. Furthermore, gas chromatography (GC) measurements showed a decrease in the peaks originating from each monomer in the reaction solution before and after the reaction, confirming that each monomer was introduced into the polymer.

[0293] (Synthesis of raw material polymer 5) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 86.62 g of a 75% toluene solution of 2-norbornene (equivalent to 64.97 g of 2-norbornene, 0.690 mol), maleic anhydride (MAN, 112.77 g, 1.150 mol), 63.56 g of 5-norbornene-2-carboxylic acid (0.460 mol), and 232.48 g of methyl ethyl ketone (MEK) were added and stirred until dissolved. Next, dissolved oxygen in the system was removed by nitrogen bubbling, and the system was heated until the internal temperature reached 80°C. Then, a solution of dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.59 g, 0.046 mol) and PEMP (22.48 g, 0.046 mol) dissolved in 68.70 g of MEK was added over 1 hour. The reaction was then carried out at 80°C for a further 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 2536.4 g of methanol to precipitate a white solid. The obtained white solid was then washed with 2634.1 g of methanol and vacuum-dried at 120°C to obtain 170.1 g of polymer (raw material polymer 5) comprising structural units derived from 2-norbornene, structural units derived from 5-norbornene-2-carboxylic acid, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 3,200, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.82. 1 The acid value of raw material polymer 5, calculated by 1H-NMR measurement, was 79 mgKOH / g, confirming that a carboxyl group derived from 5-norbornene-2-carboxylic acid was introduced into raw material polymer 5. Furthermore, gas chromatography (GC) measurements showed a decrease in the peaks originating from each monomer in the reaction solution before and after the reaction, confirming that each monomer was introduced into the polymer.

[0294] 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 then analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 1H-NMR measurements were performed. 1 The amount of carboxyl groups is determined by using the integral value of the 4H peak (around 8.1 ppm) of the phenyl group of the dimethyl terephthalate, an internal standard in 1H-NMR measurements, as a reference, and then using the integral value of the H peak (around 12.4 ppm) of the carboxyl group (-COOH) of the polymer. From this amount, the acid value (mgKOH / g) can be calculated. A higher acid value indicates a greater amount of carboxyl groups per unit mass of polymer.

[0295] The amount of sulfur in the obtained raw material polymers 4 and 5 was confirmed by elemental analysis using flask combustion and ion chromatography, and it was confirmed that sulfur was present in raw material polymer 4. In addition, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0296] For raw material polymers 2 and 3, the amount of each monomer in the reaction solution before and after the reaction was measured by gas chromatography (GC), and the consumption of each monomer was calculated to determine the ratio of each monomer introduced into the raw material polymer. Table 1 below shows the charge ratio of monomers used in the synthesis of the raw material polymer, the ratio of monomers introduced into the raw material polymer, the weight-average molecular weight (Mw) and heterodispersity (Mw / Mn) of the raw material polymer. The measurement conditions for gas chromatography 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 30m, film thickness 0.25μm (Shimadzu GLC Co., Ltd.) • Evaporation chamber temperature: 210℃ Column flow rate: 0.64 mL / min • Column heating conditions: Hold at 50°C for 5 minutes, heat at 20°C / min up to 300°C, hold at 300°C for 10 minutes.

[0297] [Table 1]

[0298] <Synthesis of Polymer P> Polymer P was prepared using the following method.

[0299] (Preparation Example 1) Polymer P1 was prepared by ring-opening the MA units of raw material polymer 1 with a monofunctional (meth)acrylic compound. Details are described below. First, 18.44 g of MEK was added to 10.00 g of raw material polymer 1 (calculated from the amount of raw material polymer 1 used, equivalent to 0.052 moles of MA) to prepare a solution. Next, 9.38 g (0.065 moles) of 4-HBA was added to this solution, followed by 3.00 g (0.030 moles) of triethylamine. The mixture was reacted at 70°C for 6 hours to prepare the reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase. The polymer was then purified by the reprecipitation method described below. • Reprecipitation method: The polymer was reprecipitation with an excess amount of water. The polymer powder obtained by reprecipitation was washed twice with an excess amount of water. The resulting reaction product was dried at 40°C for 12 hours. Based on the above, 8.7 g of polymer P1 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 1 with 4-HBA. The obtained polymer P1 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P1 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P1 did not contain any unreacted monofunctional (meth)acrylic compound.

[0300] (Preparation Example 2) 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. Details are described below. First, a solution was prepared by adding 99.93g of MEK to 60.00g of raw material polymer 1 (calculated from the amount of raw material polymer 1 used, equivalent to 0.312 moles of MA). Next, 77.49g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 56.27g (0.390 moles) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours to prepare the reaction solution. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, 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. Further liquid-liquid extraction and subsequent solvent replacement were performed according to the following procedure. • 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 resulting reaction mixture was subjected to solvent removal under reduced pressure at 50°C using a rotary evaporator. The solvent removal process was stopped when the solid content of the polymer solution was confirmed to be 27±2% by mass, as measured by a heat-drying moisture meter. Then, PGMEA was added to bring the solid content to 18% by mass and mixed until homogeneous. The same procedure was repeated two more times: solvent removal under reduced pressure at 50°C, adjusting the solid content to 27±2% by mass as measured by a heat-drying moisture meter, then adding PGMEA to bring the solid content to 18% by mass and mixing until homogeneous. Subsequently, solvent removal or the addition of PGMEA was performed, and the mixture was stirred until homogeneous, to bring the solid content to 30±3% by mass. Through these operations, the solvent used in the reaction was removed and replaced with PGMEA. Further purification was then carried out according to 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. The polymer powder, after being washed twice as described above, was washed three times with an excess amount of water. The resulting reaction product was dried at 40°C for 12 hours. Based on the above, 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 obtained polymer P2 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P2 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P2 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P2 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0301] (Preparation Example 3) Except for using 60.00g of raw material polymer 2 (0.309 moles in MA equivalent, calculated from the amount of raw material polymer 2 used) instead of raw material polymer 1, polymer P3 was prepared in the same manner as in Preparation Example 2 by ring-opening the MA units of raw material polymer 2 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P3 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P3 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P3 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 131C-NMR measurements confirmed that polymer P3 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0302] (Preparation Example 4) Except for using 60.00g of raw material polymer 3 (0.232 moles in MA equivalent calculated from the amount of raw material polymer 3 used) instead of raw material polymer 1, polymer P4 was prepared in the same manner as in Preparation Example 2 by ring-opening the MA units of raw material polymer 3 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P4 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P4 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the resulting polymer P7 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P4 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0303] (Preparation Example 5) Polymer P5 was prepared in the same manner as in Preparation Example 1, except that 10.00 g of raw material polymer 4 (0.037 moles in MA equivalent, calculated from the amount of raw material polymer 4 used) was used instead of raw material polymer 1, and the MA units of raw material polymer 4 were ring-opened with a monofunctional (meth)acrylic compound. The obtained polymer P5 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P5 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P5 did not contain any unreacted monofunctional (meth)acrylic compound.

[0304] (Preparation Example 6) Polymer P6 was prepared in the same manner as in Preparation Example 2, except that 60.00g of raw material polymer 4 (0.298 moles in MA equivalent, calculated from the amount of raw material polymer 4 used) was used instead of raw material polymer 1, and 58.12g of A-TMM-3LM-N and 100.30g of MEK were used, and the MA units of raw material polymer 4 were opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to produce polymer P6. The obtained polymer P6 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P6 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P6 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P6 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0305] (Preparation Example 7) Except for the absence of the steps of reprecipitation and washing of the polymer with excess toluene and washing with excess water after the solvent substitution step with PGMEA, the procedure was the same as in Preparation Example 6 to obtain polymer P7, in which the structural units derived from maleic anhydride in the raw material polymer 4 were ring-opened with A-TMM-3LM-N, 4-HBA and water, and a resin mixture (polymer solution P7) containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA. The obtained polymer solution P7 was analyzed by gel permeation chromatography to determine the amounts of polymer P7, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds in the solution, as well as the weight-average molecular weight and polydispersity of polymer P7. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P7 in the 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 the HLC-8320GPC EcoSEC from Tosoh Corporation. The column temperature was set to 40.0°C and the pump flow rate to 0.350 mL / min. • Peak position (holding time) Polymer P7: Peaks detected before 20 minutes (peaks with shorter retention times and higher molecular weights than A-TMM-3LM-N and 4-HBA) A-TMM-3LM-N: Total of two peaks at 20.0-20.6 minutes and 20.6-21.5 minutes. 4-HBA: 21.7~22.4 minutes • Measurement conditions: Analysis was performed using a differential refractive index detector (RI detector).

[0306] (Preparation Example 8) A resin mixture (polymer solution P8) containing polymer P8, obtained by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared. Details are described below. First, a solution was prepared by adding 99.93g of MEK to 60.00g of raw polymer 4 (calculated as 0.298 moles of MA based on the amount of raw polymer 4 used). Next, 77.49g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 56.27g (0.390 moles) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours to prepare the reaction solution. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, 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. Further liquid-liquid extraction was performed by diluting the reaction solution with MEK again, then adding a water / methanol mixed solvent and treating the solution to remove the aqueous phase. This process was then repeated once more. Finally, solvent replacement was carried out using the same procedure as in Preparation Example 2. As a result, polymer P8 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 4 with A-TMM-3LM-N, 4-HBA, and water, and a resin mixture (polymer solution P8) containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained. The obtained polymer solution P8 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 7 to determine the amounts of polymer P8, 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 P8. The results are shown in Table 2.

[0307] (Preparation Example 9) A resin mixture (polymer solution P9) containing polymer P9, obtained by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 8, except that 12.00 g (0.666 mol) of water was used. The obtained polymer solution P9 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 7 to determine the amounts of polymer P9, 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 P9. The results are shown in Table 2.

[0308] (Preparation Example 10) A resin mixture (polymer solution P10) containing polymer P10, obtained by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 8, except that 24.00 g (1.332 mol) of water was used. The obtained polymer solution P10 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 7 to determine the amounts of polymer P10, 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 P10. The results are shown in Table 2.

[0309] (Preparation Example 11) A resin mixture (polymer solution P11) containing polymer P11, obtained by ring-opening the MA units of raw material polymer 5 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 8, except that 60.00 g of raw material polymer 5 (0.286 moles in MA equivalent, calculated from the amount of raw material polymer 5 used) was used instead of raw material polymer 4. The obtained polymer solution P11 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 7 to determine the amounts of polymer P11, 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 P11. The results are shown in Table 2.

[0310] (Preparation Example 12) A resin mixture (polymer solution P12) containing polymer P12, obtained by ring-opening the MA units of raw material polymer 5 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 11, except that 24.00 g (1.332 mol) of water was used. The obtained polymer solution P12 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 7 to determine the amounts of polymer P12, 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 P12. The results are shown in Table 2.

[0311] (Preparation Example 13) The MA units of raw material polymer 6 were ring-opened with a trifunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound, further ring-opening was performed by adding water, and then polymer P13 was prepared by reacting with an epoxy group-containing (meth)acrylic compound (GMA). Details are described below. First, 166.62 g of MEK was added to 60 g of raw polymer 4 (calculated as 0.298 mol in MA equivalent from the amount of raw polymer 4 used) to prepare a solution. Next, 38.75 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 56.27 g (0.390 mol) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours to prepare a reaction solution. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added, and the mixture was reacted at 70°C for 2 hours. Subsequently, 13.31 g (0.094 mol) of GMA was added, and the mixture was reacted at 70°C for 4 hours to prepare a reaction solution. The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase. The polymer was then purified using the same reprecipitation method as in Preparation Example 2. Based on the above, polymer P13 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 4 with A-TMM-3LM-N, 4-HBA, and water, and reacting them with GMA. GPC analysis of polymer P13 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic compound and epoxy group-containing (meth)acrylic compound used. This confirmed that the obtained polymer P13 does not contain unreacted (meth)acrylic compounds, (meth)acrylic compounds without hydroxyl groups, or unreacted epoxy group-containing (meth)acrylic compounds.

[0312] (Preparation Example 14) Polymer P14 was prepared by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound and water. Details are described below. First, 60.00 g of raw polymer 4 (calculated as 0.298 moles in MA equivalent based on the amount of raw polymer 4 used) was mixed with 100.30 g of MEK to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, 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. Further liquid-liquid extraction as described in Preparation Example 2 was performed, followed by solvent replacement. Subsequently, the product was further purified by the same reprecipitation method as in Preparation Example 2. Based on the above, polymer P14 was prepared by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound and water. The obtained polymer P14 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P14 confirmed the disappearance of the peak of the polyfunctional (meth)acrylic compound used. This confirmed that the obtained polymer P14 did not contain any unreacted polyfunctional (meth)acrylic compound. Also 131C-NMR measurements confirmed that polymer P14 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N and water.

[0313] (Preparation Example 15) A resin mixture (polymer solution P15) containing polymer P15, obtained by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound and water, was prepared. Details are described below. First, a solution was prepared by adding 99.93g of MEK to 60.00g of raw polymer 4 (calculated as 0.298 moles of MA based on the amount of raw polymer 4 used). Next, 77.49g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70°C for 2 hours. The resulting reaction solution was diluted with MEK, and the aqueous phase was removed from the reaction solution by treating it with aqueous formic acid and aqueous citric acid solutions. Further liquid-liquid extraction and solvent replacement were performed in the same manner as in Preparation Example 8. This allowed us to prepare a resin mixture (polymer solution P15) containing polymer P15, which is obtained by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound and water.

[0314] The obtained polymer solution P15 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 7 to determine the amount of polymer P15 and free polyfunctional (meth)acrylic compound 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 compound is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compound relative to the peak area of ​​polymer P15 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0315] (Evaluation of physical properties) The acid value and double bond equivalent of each polymer P prepared in Preparation Examples 3-6 and 13 were measured by the following method.

[0316] (Acid value) 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 then analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 1H-NMR measurements were performed. 1 The amount of carboxyl groups is determined by using the integral value of the 4H peak (around 8.1 ppm) of the phenyl group of the dimethyl terephthalate, an internal standard in 1H-NMR measurements, as a reference, and then using the integral value of the H peak (around 12.4 ppm) of the carboxyl group (-COOH) of the polymer. From this amount, the acid value (mgKOH / g) can be calculated. A higher acid value indicates a greater amount of carboxyl groups per unit mass of polymer. The results are shown in Table 2. An acid value of 50 gKOH / g or higher indicates that the polymer contains sufficient carboxyl groups necessary for adequate development.

[0317] (double bond equivalent) The double bond equivalent of polymer P was measured by the following method. Similar to the above method for measuring acid value, 1¹H-NMR measurements were performed. The amount of acryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal originating from acryloyl groups (5.6-5.8 ppm, 3H) and the signal of the phenyl group of the internal standard (8.1 ppm, 4H) in the obtained spectral chart. The amount of methacryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal originating from methacryloyl groups (5.6-5.8 ppm, 2H) and the signal of the phenyl group of the internal standard (8.1 ppm, 4H). Here, the signal originating from methacryloyl groups at 6.0-6.1 ppm was negligible and overlapped with the signal of acryloyl groups, so it was calculated as the signal of acryloyl groups. The amount of double bonds (mol / g) was calculated from the sum of the calculated amount of acryloyl groups (mol / g) and methacryloyl groups (mol / g) in the polymer, and the double bond equivalent (g / mol) was calculated from the double bond amount. 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 polymer.

[0318] [Table 2] [Table 3]

[0319] (Examples 1-11, Comparative Examples 1-4) In each example and comparative example, a resin composition was prepared and evaluated for the following items. <Rating> [Alkali dissolution rate of resin compositions] Polymers P1-P6, P13, and P14 obtained in Preparation Examples 1-6, 13, and 14 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1-6, 13, and 14 with a solid content concentration of 30% by mass. Next, resin compositions 7-12 and 15, consisting of polymer solutions P7-P12 and P15 obtained in the above resin compositions 1-6, 13, and 14 or preparation examples 7-12 and 15, were spin-coated onto the wafer, the PGMEA was dried, and then the film was pre-baked at 100°C for 2 minutes to produce a resin film with a thickness of approximately 2 μm. The resin film, along with the wafer, was immersed in a 2% sodium carbonate aqueous 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 then dividing the film thickness by that time. The results are shown in Table 3. If the alkali dissolution rate is 200 nm / s or higher, it can be used without problems as a photosensitive material; if it is 300 nm / s or higher, it can be considered to have good developability; if it is 400 nm / s or higher, it can be considered to have even better developability; and if it is 500 nm / s or higher, it can be considered to have particularly good developability.

[0320] [Sensitivity evaluation of photosensitive resin composition (exposure amount at which the residual film rate is 90% 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 solids content concentration was 30% by mass. Polymers P1-P6, P13, P14 (polymers P from Preparation Examples 1-6, 13, and 14, respectively) or resin compositions 7-12, 15 (polymer solutions P7-P12 and P15 from Preparation Examples 7-12 and 15, respectively): 100 parts by mass (Here, resin compositions 7-12 and 15 were weighed so that the solid content (total amount of polymers P7-P12, P15 and polyfunctional (meth)acrylic compound) was 100 parts by mass.) • Polyfunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-DPH): 50 parts by mass • Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by mass • Adhesion enhancer (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass • Surfactant (manufactured by DIC Corporation, F-556): 0.5 parts by mass

[0321] The obtained photosensitive resin composition was rotary coated onto a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds to obtain a thin film A with a thickness of approximately 3.0 μm (±0.3 μm). This thin film A is subjected to a 100 mJ / cm² radiation dose using a Canon g+h+i-ray mask aligner (PLA-501F) via a photomask with a light-shielding rate of 1-100%. 2 The g+h+i line was exposed with the specified exposure dose. After exposure, the thin film is developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (wafer immersion) to achieve a radiation level of 1-100 mJ / cm². 2 Thin films B were obtained by exposing and developing them at each exposure level. The residual film percentage was calculated from the film thicknesses of thin films A and B obtained by the above method using the following formula. Residual film percentage (%) = (Film thickness of thin film B at each exposure dose / Film thickness of thin film A) × 100 The exposure dose at which a residual film rate of 90% or more was determined as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. The exposure dose at which a residual film rate of 90% or more was 50 mJ / cm² 2 If the following conditions are met, it can be used without problems as a photosensitive composition, up to 20 mJ / cm². 2 The sensitivity can be considered good if it is below 15 mJ / cm². 2 The following can be considered better, and even better, 12 mJ / cm². 2 The following can be considered particularly good.

[0322] [Alkaline dissolution rate of photosensitive resin composition (2.0% by mass sodium carbonate aqueous solution)] The photosensitive resin composition prepared in the sensitivity evaluation described above was spin-coated onto a wafer, the PGMEA was dried, and then a resin film with a thickness of approximately 2 μm was fabricated by pre-baking at 100°C for 2 minutes. The resin film, along with the wafer, was immersed in a 2% sodium carbonate aqueous 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 then dividing the film thickness by that time. The results are shown in Table 3. If the alkali dissolution rate is 500 nm / s or higher, it can be used without problems as a photosensitive material; if it is 700 nm / s or higher, it can be considered to have good developability; if it is 900 nm / s or higher, it can be considered to have even better developability; and if it is 1000 nm / s or higher, it can be considered to have particularly good developability.

[0323] [Yellow Index] The photosensitive resin composition prepared in the sensitivity evaluation described above was rotary coated onto Eagle XG glass (Corning, 0.5 mm thick) and baked on a hot plate at 100°C for 120 seconds to obtain a thin film with a thickness of approximately 3.0 μm (±0.1 μm). This thin film was subjected to a 100 mJ / cm² radiation dose using a Canon g+h+i-line mask aligner (PLA-600F). 2 The g+h+i line was exposed with the specified exposure dose. After exposure, the thin film is developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (wafer immersion) to achieve a radiation level of 100 mJ / cm². 2 A thin film was obtained by exposing and developing it with the specified exposure level. The thin film was heat-treated at 230°C for 30 minutes under air conditions. After the thin film was cooled under air conditions at room temperature, it was heat-treated again at 230°C for 30 minutes under air conditions. The same procedure was repeated, and the heat treatment under air for 30 minutes was performed a total of three times. The yellow index (YI) of the thin film obtained by the above method was measured three times at different measurement points using a CR-5 colorimeter (manufactured by Konica Minolta), and the average value was taken as the YI value. The measurement type was transmission measurement, and 100% calibration was performed using uncoated Eagle XG glass (manufactured by Corning, thickness 0.5 mm). The results are shown in Table 3. If the yellow index is 1.30 or less, it can be used without problems as a photosensitive material, if it is 1.20 or less, it can be considered to have good heat discoloration resistance, if it is 1.15 or less, it can be considered to have even better resistance, and if it is 1.10 or less, it can be considered to have particularly good resistance.

[0324] The results of the developability evaluation, sensitivity evaluation, and heat discoloration resistance evaluation are shown in Table 3.

[0325] [Table 4]

[0326] The photosensitive resin compositions containing the polymers of Examples 1 to 11 had a good balance of alkali solubility, sensitivity, and heat discoloration resistance. The photosensitive resin compositions of Examples 2 to 11, which contained polymers having structural units derived from norbornenecarboxylic acid and a ring-opened structure with a polyfunctional (meth)acrylic compound, had a lower exposure amount at which a residual film rate of 90% or more was achieved, and exhibited particularly excellent sensitivity.

[0327] <Making color filters / spacers> To the photosensitive resin compositions prepared in Examples 1 to 11, an appropriate amount of pigment dispersion NX-061 (manufactured by Dainichi Seika Kogyo Co., Ltd., green) was added to prepare a colored photosensitive resin composition. By forming this film on a substrate and then performing processes such as exposure and alkaline development, we were able to create a green color filter and spacer. Furthermore, by using NX-053 (blue) or NX-032 (red), also manufactured by the same company, as pigment dispersions instead of NX-061, it was possible to form blue or red color filters and spacers.

[0328] <Creation of Black Matrix / Black Bank / Black Spacer> To the photosensitive resin compositions prepared in Examples 1 to 11, an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichi Seika Kogyo Co., Ltd.) was added to prepare a black photosensitive resin composition. By depositing this onto a substrate and performing processes such as exposure and alkaline development, we were able to form a black matrix / black bank / black spacer. [Explanation of Symbols]

[0329] 10 circuit boards 11 Black Matrix 12 Color Filters 13 Protective film 14 Transparent electrode layer

Claims

1. A structural unit represented by formula (NB), A structural unit represented by formula (NC), A structural unit represented by formula (1-2) and at least one structural unit selected from the structural units represented by formula (1-3), A polymer containing, 【Chemistry 1】 In equation (NB), R １ , R ２ , R ３ and R ４ is a hydrogen atom, and a １ is 0, 1, or 2, 【Chemistry 2】 In formula (NC), R １１ , R １２ , R １３ and R １４ at least one of which is a -Z-COOH group, where Z is a single bond, -CH ２ -, or -(CH ２ ) ２ -, and the other R １１ , R １２ , R １３ and R １４ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and a １１ is 0, 1 or 2, 【Transformation 3】 In formula (1-2), R ｐ R is a group having two or more (meth)acryloyl groups, ２２ This is a hydrogen atom or an organic group having 1 to 3 carbon atoms. 【Chemistry 4】 In formula (1-3), R ｓ This is a group having one (meth)acryloyl group, R ２２ This is a hydrogen atom or an organic group having 1 to 3 carbon atoms. polymer.

2. The polymer according to claim 1, It further includes the structural unit represented by formula (1-1), 【Transformation 5】 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 substituted or unsubstituted alkylene group with 1 to 4 carbon atoms, When Q is the alkyl group and X is the alkylene group, Q and X may condense to form a cyclic group. R ２１ A polymer is a polymer consisting of a hydrogen atom or an organic group with 1 to 3 carbon atoms.

3. The polymer according to claim 1, It further includes structural units represented by formula (1-4), 【Transformation 6】 In formula (1-4), R ２２ A polymer is a polymer consisting of a hydrogen atom or an organic group with 1 to 3 carbon atoms.

4. The polymer according to claim 1, It further includes at least one selected from the structural units represented by formula (1) and the structural units represented by formula (2), 【Transformation 7】 【Transformation 8】 In formula (1), R p is a group having two or more (meth)acryloyl groups, and R 21 and R 22 are hydrogen atoms or organic groups having 1 to 3 carbon atoms. In formula (2), R s is a group having one (meth)acryloyl group, and R 21 and R 22 are a hydrogen atom or an organic group having 1 to 3 carbon atoms, forming a polymer.

5. The polymer according to claim 1, It further includes the structural unit represented by formula (3), 【Chemistry 9】 In formula (3), R ２１ and R ２２ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms.

6. The polymer according to claim 2, It further includes at least one selected from the structural units represented by formula (8) and the structural units represented by formula (9), 【Chemistry 10】 【Chemistry 11】 In equations (8) and (9), R ｐ and R ｓ , R ２１ and R ２２ A polymer in which Z, Q, and X are the same as those in formulas (1-1), (1-2), and (1-3).

7. The polymer according to claim 2, It further includes the structural unit represented by formula (5), 【Chemistry 12】 A polymer in which, in formula (5), R21 and R22 are hydrogen atoms or organic groups having 1 to 3 carbon atoms, and Z, Q, and X are the same as those in formula (1-1).

8. The polymer according to claim 2, It further includes the structural unit represented by formula (6), 【Chemistry 13】 A polymer in which R21 and R22 are hydrogen atoms or organic groups having 1 to 3 carbon atoms, and Z, Q, and X are the same as those in formula (1-1).

9. The polymer according to claim 1, It further includes structural units represented by formula (MA), 【Chemistry 14】 In formula (MA), R ２１ and R ２２ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms.

10. The polymer according to claim 1, The polymer contains structural units represented by the above formula (1-2), R in equation (1-2) ｐ is at least one selected from the group represented by formula (1b), the group represented by formula (1c), and the group represented by formula (1d), 【Chemistry 15】 In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different. X １ X is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented as -Z-X- (where Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X groups. １ They may be the same or different. X １ ' represents a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (where X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X ２ This is an organic group with 1 to 12 carbon atoms and a (k+1) valency. 【Chemistry 16】 In formula (1c), k, R, X １ and X ２ These are R, k, and X in equation (1b), respectively. １ and X ２ This is synonymous with multiple Rs, which may be the same or different from each other, and multiple X １ They may be the same or different from each other. X ３ This is a single bond or a divalent organic group having 1 to 6 carbon atoms. X ４ and X ５ Each of these is independently a single bond or a divalent organic group having 1 to 6 carbon atoms. X ６ It is a divalent organic group having 1 to 6 carbon atoms. 【Chemistry 17】 In formula (1d), n is an integer between 2 and 5. A polymer in which R is independently either a hydrogen atom or a methyl group.

11. The polymer according to claim 1, The polymer contains structural units represented by the above formula (1-3), R in the above formula (1-3) ｓ This is a base represented by formula (2a), [Chemistry 18] In formula (2a), X １０ R is a divalent organic group, and R is either a hydrogen atom or a methyl group. polymer.

12. The polymer according to claim 1, The polymer has a structure represented by formula (P), 【Chemistry 19】 In equation (P), n is an integer between 1 and 6. p, q, and r indicate the molar content of structural units A, B, and C contained in each of the n polymer chains within the brackets. p, q, and r may be the same or different for each of the n polymer chains within the brackets. 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 content of each structural unit A, B, and C contained in the polymer is, respectively, p ｔ , q ｔ , and r ｔ Therefore, p ｔ +q ｔ +r ｔ = 1, p ｔ q is greater than 0, 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 C1-C30 1-C6 valent organic group derived from monofunctional or bifunctional or multi-functional thiol group-containing compounds. A represents a structural unit represented by the above formula (NB), B includes at least one structural unit selected from the structural units represented by formula (1-2) and the structural units represented by formula (1-3), C represents a structural unit represented by the above formula (NC), A polymer in which multiple A's, B's, and C's may be identical or different.

13. The polymer according to claim 1, A polymer having a weight-average molecular weight of 3,000 or more and 15,000 or less.

14. A polymer solution comprising the polymer described in any one of claims 1 to 13.

15. The polymer solution according to claim 14, A polymer solution further comprising a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

16. The polymer solution according to claim 14, A polymer solution used for forming color filters, black matrices, spacers, or partition materials.

17. A polymer according to any one of claims 1 to 13, A photoradical polymerization initiator, Photosensitive resin composition.

18. A cured product formed from the photosensitive resin composition described in claim 17.

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