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

Abstract

To provide a polymer having high sensitivity and high alkali solubility.SOLUTION: A polymer has a structure represented by formula (P). (In the formula (P), m denotes an integer of 0-5, n is an integer of 1-6, m+n is 2-6, p, q and r each represent molar contents of A, B and C, with p+q+r=1, where p is greater than 0, q is greater than 0, r is equal to or greater than 0, and p, q and r may be the same or different for each of n constitutional units within [], X is hydrogen or a C1-30 organic group, Y is a divalent to hexavalent, C1-30 organic group induced from a di-functional or multi-functional thiol group-containing compound, A is a styrene monomer-derived constitutional unit, B includes a specific constitutional unit having a (meth)acryloyl group, C denotes a divalent constitutional unit induced from a copolymerizable compound having a double bond, and D denotes a different structure from the structure within []n).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 color filters and black matrices. Color filters and black matrices are constructed by forming structures such as colored patterns and protective films 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 Initiative] [Problems that the invention aims to solve]

[0004] Photosensitive resin compositions used to form color filters and black matrices utilize resins that undergo polymerization reactions and harden upon exposure to light. Color filters and black matrices 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 the exposure time required, thereby improving productivity. Furthermore, photosensitive resin compositions are required to exhibit excellent processability in development processes using alkaline developers. In addition, the hardened product of the photosensitive resin composition is required to have 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, a polymer having a structure represented by formula (P) is provided.

[0007] [ka] (In equation (P), m is 0, n is an integer between 1 and 6. p is greater than 0, q is greater than 0, and r is 0. p represents the molar content of A, q represents the molar content of B, and p + q = 1. X is hydrogen, Y is an organic group having a thioether group, which is a 1-6 valent organic group derived from at least one selected from two or more thiol group-containing compounds represented by formula (s-1) to (s-21), and the organic group having the thioether group is bonded to the structural unit in [ ]n via the thioether group (*-S-* (* is a bond)) derived from the thiol group-containing compound, A represents a structural unit represented by formula (ST), B includes at least one structural unit selected from the structural units represented by formula (5), formula (6), formula (8), and formula (9). fruit, The structural units A and B are arranged randomly or alternately. .

[0008] [ka] (In equation (ST), R 1 , R 2 , and R 3 Each of these is independently either a hydrogen atom or an organic group with 1 to 30 carbon atoms.

[0009] [ka]

[0010] [ka]

[0011] [ka] [ka] (In equations (5), (6), (8), and (9), R p This represents a group containing two or more (meth)acryloyl groups, R s This represents a group containing one (meth)acryloyl group, 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, If Q is the alkyl group and X is the alkylene group, Q and X may condense to form a cyclic group. ) [ka]

[0012] Furthermore, according to the present invention, a polymer solution containing the above-mentioned polymer is provided.

[0013] Furthermore, the present invention provides a photosensitive resin composition comprising the above-mentioned polymer solution and a photopolymerization initiator.

[0014] Furthermore, the present invention provides a cured product of the above-mentioned photosensitive resin composition. [Effects of the Invention]

[0015] The present invention provides a polymer as a resin material for use in a photosensitive resin composition that has good sensitivity, high alkali solubility, and therefore excellent developability, as well as reduced yellowing and therefore high heat resistance to discoloration. [Brief explanation of the drawing]

[0016] [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. [Modes for carrying out the invention]

[0017] 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".

[0018] 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.

[0019] 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.

[0020] [Polymer P] (First embodiment) The polymer of this embodiment (hereinafter referred to as "polymer P") has a structure represented by the following general formula (P). Polymer P has a structure in which a polymer chain, typically composed of structural units A and B, is bonded to a 2- to 6-valent organic group having 1 to 30 carbon atoms, derived from a thiol group-containing compound with two or more functionalities represented as "Y" in the formula.

[0021] [ka] In general formula (P), m is preferably 0 or 1, and more preferably 0. n is an integer between 1 and 6, preferably between 3 and 6. However, n+m is between 2 and 6, preferably between 3 and 6. p is greater than 0, preferably between 0.25 and 0.75. q is greater than 0, preferably between 0.25 and 0.75. r is 0 or greater, preferably 0 to 0.5, more preferably 0 to 0.3, and particularly preferably 0 to 0.1. 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 having between 1 and 30 carbon atoms. Y is a 2- to 6-valent organic group (i) having 1 to 30 carbon atoms derived from a thiol group-containing compound with two or more functionalities, and it is bonded to the structural units in [ ]n and [ ]m via a thioether group derived from the thiol group. A represents a structural unit expressed by formula (ST). B includes at least one structural unit selected from the structural units represented by formula (1), formula (2), and formula (3). C contains a divalent structural unit derived from copolymerizable compounds having a double bond. Multiple instances of A, B, or C may be identical or different. In general formula (P), the order in which A, B, and C are combined is not particularly limited, and any of A, B, or C may be combined with Y. D represents a structure different from the structure within [ ]n, and D may contain any of A, B, or C.

[0022] [ka] (In equation (ST), R 1 , R 2 , and R 3 Each of these is independently either a hydrogen atom or an organic group with 1 to 30 carbon atoms.

[0023]

Chem.

[0024]

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[0025]

Chem.

[0026] The polymer P of this embodiment has a structure in which a polymer chain, typically composed of structural units A and B, is bonded to a 2- to 6-valent organic group having 1 to 30 carbon atoms, derived from a thiol group-containing compound with two or more functionalities represented as "Y" in formula (P). Due to the presence of a thioether group, polymer P has excellent sensitivity in photolithography and higher alkali solubility, thus providing a resin cured product with superior developability.

[0027] The polymer P of this embodiment also includes, as structural unit B, at least one of the structural units represented by general formula (1), general formula (2), and general formula (3). In other words, polymer P has a structural unit having at least one (meth)acryloyl group as an essential component. As a result, the photosensitive resin composition containing polymer P has excellent sensitivity when subjected to photolithography. This is thought to be because the (meth)acryloyl group contained in the structural units represented by general formulas (1) to (3) promotes the curing reaction (polymerization reaction).

[0028] Furthermore, polymer P contains a styrene-derived structural unit A represented by the general formula (ST). This structural unit (ST) is chemically robust. Therefore, polymer P containing this structural unit exhibits minimal weight loss and stability when subjected to heat treatment. Thus, photosensitive resin compositions containing polymer P can be suitably used to manufacture films and filters for use in liquid crystal display devices and solid-state image sensors where heat resistance is required.

[0029] In one embodiment, polymer P may include, as structural unit B, the structural unit represented by formula (4) in addition to the structural units represented by formulas (1) to (3). By including the structural unit represented by formula (4), polymer P has high alkali solubility. As a result, a photosensitive resin composition containing such polymer P exhibits excellent developability when subjected to photolithography treatment using an alkaline aqueous solution as the developer.

[0030] [ka]

[0031] In one embodiment, polymer P may include structural units C derived from monomers polymerizable with respect to styrene and maleic anhydride. Structural units C are, for example, substituted or unsubstituted structural units derived from norbornene, indene, maleimide, or norbornadiene. Substituents that these monomers may have include alkyl groups, aryl groups, etc. More specifically, substituted maleimides include cyclohexylmaleimide and phenylmaleimide.

[0032] Preferably, structural unit C includes a structural unit represented by general formula (11) (a divalent structural unit derived from substituted or unsubstituted norbornene), a structural unit represented by general formula (12) (a divalent structural unit derived from substituted or unsubstituted maleimide), a structural unit represented by general formula (13) (a divalent structural unit derived from substituted or unsubstituted indene), or a structural unit represented by general formula (14) (a divalent structural unit derived from substituted or unsubstituted norbornadiene).

[0033] [ka]

[0034] In general formula (11), R 1 ~R 4 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and a1 is either 0 or 1. In general formula (12), R 3 R represents a hydrogen atom, an alkyl group, or an aryl group. In general formula (13), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group, or an aryl group. In general formula (14), R 7 ~R 10 Each of these independently represents a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms.

[0035] In the structural unit represented by the general formula (ST) that constitutes polymer P, R 1 , R 2 , and R 3 Organic groups having 1 to 30 carbon atoms that can constitute these include substituted or unsubstituted, linear or branched alkyl groups having 1 to 30 carbon atoms. More specifically, these include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalil groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxyl groups.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] R in structural units represented by general formula (ST) 1 and R 2 As such, a hydrogen atom or an alkyl group is preferred, a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom is particularly preferred. R in the structural unit represented by general formula (ST) 3 R is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms.1 and R 2 , and R 3 By appropriately selecting R, the alkali solubility of the resulting polymer P can be adjusted. For example, R 3 By using a lower alkyl group, the alkali solubility of the resulting polymer P can be controlled. Note, R 1 and R 2 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 , and R 3 As the organic group having 1 to 30 carbon atoms, alkyl groups such as fluoride may be selected.

[0040] The proportion of structural units represented by general formula (ST) in the total structural units of polymer P is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%.

[0041] In a structural unit represented by general formula (1) that can constitute polymer P, R p R is a group containing two or more (meth)acryloyl groups, preferably a group containing 2 to 6 (meth)acryloyl groups, and more preferably a group containing 3 to 5 (meth)acryloyl groups. p By optimizing the number of (meth)acryloyl groups contained in the polymer P, the sensitivity of the polymer P in 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. Additionally, the heat resistance of polymer P can be improved.

[0042] R in general formula (1) p Preferably, the group is represented by general formula (1b), general formula (1c), or general 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.

[0043] [ka]

[0044] 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 2 It is a k+1 valent organic group with 1 to 12 carbon atoms. 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.

[0045] 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).

[0046] 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)-.

[0047] 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.

[0048] X 2 As a k+1 valent organic group having 1 to 12 carbon atoms, 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. X 2 This group is, for example, a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms) from which k+1 hydrogen atoms have been removed. More preferably, it is a linear hydrocarbon having 1 to 3 carbon atoms from which k+1 hydrogen atoms have been removed. The hydrocarbon here may contain oxygen atoms (e.g., ether bonds or hydroxyl groups). Furthermore, the hydrocarbon is preferably a saturated hydrocarbon. In another form, X 2 The group may include a cyclic structure. Examples of groups including a cyclic structure include groups including an alicyclic structure and groups including a heterocyclic structure (for example, an isocyanuric acid structure).

[0049] [ka]

[0050] In formula (1c), k, R, X 1 and X 2 These are R, k, and X in equation (1b), respectively. 1 and X2 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 It is 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.

[0051] R, k, X 1 and X 2 The specific embodiments and preferred embodiments are the same as those described in general formula (1b). X 3 and X 6 Examples of divalent organic groups having 1 to 6 carbon atoms include groups obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. The hydrocarbon here may also contain oxygen atoms (e.g., ether bonds or hydroxyl groups). Furthermore, the hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 Examples of divalent organic groups having 1 to 6 carbon atoms include linear or branched alkylene groups. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

[0052] [ka]

[0053] In equation (1d), n is an integer between 2 and 5, preferably 2 or 3. The specific and preferred forms of R are the same as those described in general formula (1b).

[0054] When polymer P contains structural units represented by general formula (1), the proportion of structural units represented by general formula (1) in the total structural units of polymer P is preferably 3 to 40 mol%, more preferably 3 to 30 mol%.

[0055] In a structural unit represented by general formula (2) that can constitute polymer P, R S This group contains only one (meth)acryloyl group. In particular, in the design of typical photosensitive resin compositions, when curability is increased to increase sensitivity, curing tends to progress too much, resulting in poor developability. On the other hand, when developability is improved, curing tends to be insufficient. Therefore, it is preferable that polymer P contains either or both of the structural units represented by general formula (1) and / or general formula (2), thereby achieving a good balance between sensitivity and developability.

[0056] R S This is a group represented, for example, by the following formula (2a).

[0057] [ka]

[0058] In equation (2a), X 10 R is a divalent organic group, and R is either a hydrogen atom or a methyl group. X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. In equation (2a), X 10 R is a divalent organic group, and R is either a hydrogen atom or a methyl group. X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. X 10A 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.

[0059] 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 readily involved in the crosslinking reaction, thereby increasing sensitivity.

[0060] 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.

[0061] When polymer P contains structural units represented by general formula (2), the proportion of structural units represented by general formula (2) in the total structural units of polymer P is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

[0062] Furthermore, if polymer P contains both structural units represented by general formula (1) and structural units represented by general formula (2), the total content of structural units represented by general formula (1) and structural units represented by general formula (2) in polymer P is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and even more preferably 10 to 40 mol%, based on the total structural units constituting polymer P.

[0063] When polymer P contains structural units represented by general formula (3), the proportion of structural units represented by general formula (3) in the total structural units of polymer P is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%.

[0064] In general formula (P), X is hydrogen or an organic group having 1 to 30 carbon atoms. An organic group having 1 to 30 carbon atoms is R in formula (ST) above. 1 , R 2 , and R 3 It is similar to the organic group having 1 to 30 carbon atoms that makes up the compound.

[0065] In general formula (P), Y is a divalent to hexavalent organic group (i) having 1 to 30 carbon atoms derived from a thiol group-containing compound with two or more functionalities. In this embodiment, the number of functional groups is the number of thiol groups. That is, the thiol group-containing compound contains two or more thiol groups, and the organic group (i) is bonded to the structural units in [ ]n and [ ]m via 1 to 6 thioether groups derived from the thiol group. The 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 can be obtained as a mixture of resins with n+m numbers (number of bonds) of 2 to 6. The organic group (i) having 1 to 30 carbon atoms is bifunctional or 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 2 to 6, preferably 2 to 6.

[0066] The 2-6 valent organic group (i) having 1 to 30 carbon atoms may contain one or more atoms selected from O, N, S, P, and Si. Examples of the 2-6 valent organic group (i) having 1 to 30 carbon atoms include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalil groups, cycloalkyl groups, alkoxy groups, and heterocyclic groups having 2 to 6 thioether groups (*-S-* (* is a bond)).

[0067] 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.

[0068] 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.

[0069] 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.

[0070] Polymer P may contain at least one structural unit selected from the structural unit represented by formula (5), formula (6), formula (8), and formula (9), as a structural unit containing one or two of the above general formulas (1), (2), and (3). By containing such structural units, polymer P may have high alkali solubility. Note that in formulas (5), (6), (8), and (9), R p , R sQ, X, and Z are equivalent to those in equations (1) to (3) above.

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] When polymer P contains structural units represented by general formula (5), the proportion of structural units represented by general formula (5) 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 contains structural units represented by general formula (6), the proportion of structural units represented by general formula (6) in the total structural units of polymer P is preferably 3 to 35 mol%, more preferably 5 to 25 mol%.

[0077] When polymer P contains structural units represented by general formula (8), the proportion of structural units represented by general formula (8) in the total structural units of polymer P is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%.

[0078] When polymer P contains structural units represented by general formula (9), the proportion of structural units represented by general formula (9) in the total structural units of polymer P is preferably 0.5 to 35 mol%, more preferably 2 to 25 mol%.

[0079] In one embodiment, polymer P may contain structural units represented by formula (10). By containing structural units represented by formula (10), polymer P has excellent alkali solubility. As a result, the photosensitive resin composition containing polymer P exhibits an excellent balance of sensitivity and developability even when subjected to photolithography processing using a strongly basic developer.

[0080] [ka]

[0081] When polymer P contains structural units represented by general formula (10), the proportion of structural units represented by general formula (10) in the total structural units of polymer P is preferably 1 to 15 mol%, more preferably 2 to 10 mol%.

[0082] In one embodiment, polymer P may contain a structural unit represented by formula (MA). The structural unit represented by general formula (MA) undergoes ring-opening with an alkaline developer to produce two carboxyl groups. Therefore, polymer P containing such a structural unit exhibits excellent developability. When polymer P contains a structural unit represented by general formula (MA), the amount of the structural unit represented by general formula (MA) in the total structural units of polymer P is preferably 1 to 35 mol%, more preferably 2 to 30 mol%.

[0083] [ka]

[0084] In general formula (P), the divalent to hexavalent organic group represented as Y is derived from compounds containing two or more thiol groups. Examples of compounds containing two or more thiol groups that can derive Y include those represented by the following chemical formulas (s-1) to (s-21).

[0085] [ka]

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[0106] A thiol group-containing compound with two or more functions may be used alone or in a mixture of two or more. In particular, a thiol group-containing compound with three to six functions (three to six valents) having three to six thiol groups in one molecule is preferred because it exhibits excellent reactivity with other monomers. In this embodiment, the thiol group-containing compound with two or more functions 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 is particularly preferably includes compounds represented by chemical formulas (s-1) to (s-3), (s-5), and (s-9). The organic group (i) Y, which has 1 to 6 valent carbon atoms and 1 to 30 carbon atoms, is bonded to the structural unit in [ ]n and / or the structural unit in [ ]m via a thioether group (-S-* (* is a bonding hand)) derived from the thiol group of these thiol group-containing compounds. The organic group (i) may have a thiol group that does not participate in bonding to the structural unit in [ ]n and the structural unit in [ ]m.

[0107] If Y in polymer P of this embodiment is an organic group derived from a tetrafunctional (tetravalent) thiol group-containing compound represented by the above-mentioned chemical formula (s-2), polymer P may have a structure represented, for example, by the following general formula (I).

[0108] [ka]

[0109] The structure of general formula (I) corresponds to the case in general formula (P) where m is 0 and n is 4. In general formula (I), A, B, C, X, p, q, and r are synonymous with those in general formula (P). The A, B, C, X, p, q, and r contained in the four structural units within the brackets [ ] may be the same or different.

[0110] In general 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 general 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.

[0111] The weight-average molecular weight Mw of polymer P is, for example, 5,000 to 80,000, preferably 6,000 to 75,000, more preferably 7,000 to 70,000, and even more preferably 8,000 to 60,000. By appropriately adjusting the weight-average molecular weight, the sensitivity and solubility in alkaline developers can be adjusted.

[0112] Furthermore, the degree of dispersion of polymer P (weight-average molecular weight Mw / number-average molecular weight Mn) 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.

[0113] The glass transition temperature of polymer P is preferably 150 to 250°C, more preferably 170 to 230°C. Polymer P has a relatively high glass transition temperature because it mainly contains structural units represented by the general formula (ST). This is advantageous in the manufacturing of liquid crystal displays and solid-state image sensors because it allows patterns formed on the substrate to exist stably. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0114] The acid value of polymer P is 70 mg KOH / g or more and 150 mg KOH / g or less, preferably 80 mg KOH / g or more and 140 mg KOH / g or less. The double bond equivalent of polymer P is 100 g / mol or more and 700 g / mol or less, preferably 200 g / mol or more and 600 g / mol or less, more preferably 200 g / mol or more and 430 g / mol or less. By having an acid value of 70 mgKOH / g or higher for polymer P, good developability can be obtained. Furthermore, by having a double bond equivalent of 700 g / mol or less, the sensitivity of the photosensitive resin composition containing polymer P can be increased.

[0115] Furthermore, if the acid value of polymer P is too high, there is a concern that the exposed areas may dissolve easily during development with an alkaline developer, resulting in a larger exposure 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 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.

[0116] By adjusting the acid value and / or double bond equivalent of polymer P, it is possible to achieve an even higher level of balance between sensitivity and developability.

[0117] The acid value and double bond equivalent of polymer P 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).

[0118] The acid value and double bond equivalent of polymer P can be adjusted to desired values ​​by appropriately designing the ratio of structural units introduced into polymer P, particularly the number of polymerizable carbon-carbon double bonds in the (meth)acryloyl groups contained in the structural units represented by formulas (1) to (3).

[0119] The content (ratio) of each structural unit contained in polymer P in this embodiment is determined by 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.

[0120] (Second Embodiment) In the second embodiment, polymer P may be a polymer obtained by polymerizing a monomer composition containing a styrene monomer represented by the following formula (STm) and maleic anhydride in the presence of a thiol group-containing compound with two or more functionalities to prepare a raw material polymer, and then reacting this raw material polymer with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst. In formula (STm), R 1 , R 2 , and R 3 This is equivalent to the one in equation (ST).

[0121] The polymer P obtained by the above method includes a structural unit represented by formula (ST) derived from styrene monomer, and a structural unit represented by formula (5) and / or formula (6) derived from maleic anhydride and a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound.

[0122] [ka]

[0123] (Third embodiment) In a third embodiment, polymer P may be a polymer obtained by polymerizing a monomer composition containing the monomer represented by the above formula (STm) and maleic anhydride in the presence of a thiol group-containing compound with two or more functionalities to prepare a raw material polymer, then reacting this raw material polymer with a polyfunctional (meth)acrylic compound and / or a monofunctional methacrylic compound in the presence of a basic catalyst to prepare a polymer precursor, and then treating this polymer precursor with water in the presence of a basic catalyst.

[0124] The polymer P obtained by the above method includes a structural unit represented by formula (ST) derived from styrene monomer, a structural unit represented by formula (5) and / or formula (6) derived from maleic anhydride and a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound, and a structural unit represented by formula (10) derived from the reaction of maleic anhydride and water.

[0125] (Fourth embodiment) In the fourth embodiment, polymer P may be a polymer obtained by polymerizing a monomer composition containing the monomer represented by the above formula (STm) and maleic anhydride in the presence of a thiol group-containing compound with two or more functionalities, then reacting this raw material polymer with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst to prepare a polymer precursor, and then reacting this polymer precursor with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst.

[0126] The polymer P obtained by the above method includes a structural unit represented by formula (ST) derived from a styrene monomer, a structural unit represented by formula (5) and / or formula (6) derived from maleic anhydride and a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound, and a structural unit represented by formula (7) and / or formula (8) derived from maleic anhydride and a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound and an epoxy group-containing (meth)acrylic compound.

[0127] [Method for producing polymer P] The method for producing polymer P in this embodiment will be explained using the methods for producing polymer P in the second, third, and fourth embodiments described above as examples.

[0128] (Method for producing polymer P according to the second embodiment) The polymer P of the second embodiment, which includes the structural unit represented by formula (5) and / or the structural unit represented by formula (6), Step (I): A step of preparing a raw material polymer containing a structural unit represented by general formula (ST), a structural unit represented by general formula (MA), and the aforementioned organic group (i) having 1 to 6 valent carbon atoms with 1 to 30 carbon atoms, and Step (II): The polymer can be produced by reacting the raw material polymer obtained in Step (I) with 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") in the presence of a basic catalyst to prepare a polymer P that contains a structural unit represented by general formula (ST), the aforementioned organic group (i) having 1 to 6 valent carbon atoms with 1 to 30 carbon atoms, and a structural unit represented by general formula (5) and / or a structural unit represented by general formula (6), and optionally further containing a structural unit represented by general formula (MA).

[0129] In step (II), 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, and then react the resulting reaction mixture with the monofunctional (meth)acrylic compound.

[0130] (Method for producing polymer P according to the third embodiment) The polymer P of the third embodiment, which includes the structural unit represented by formula (5) and / or the structural unit represented by formula (6), and the structural unit represented by formula (10), Step (I): A step of preparing a raw material polymer containing a structural unit represented by general formula (ST), a structural unit represented by general formula (MA), and the aforementioned organic group (i) having 1 to 6 valent carbon atoms with 1 to 30 carbon atoms, and Step (II): A step to prepare a polymer precursor containing a structural unit represented by general formula (ST), the aforementioned organic group (i) having 1 to 6 valent carbon atoms and 1 to 30 carbon atoms, a structural unit represented by general formula (5) and / or a structural unit represented by general formula (6), and a structural unit represented by general formula (MA), by reacting the raw material polymer obtained in step (I) with a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as a "polyfunctional (meth)acrylic compound") in the presence of a basic catalyst. Step (IIIa): The polymer can be produced by treating the polymer precursor obtained in Step (II) with water in the presence of a base catalyst to prepare a polymer P containing a structural unit represented by general formula (ST), the aforementioned organic group (i) having 1 to 6 valent carbon atoms with 1 to 30 carbon atoms, a structural unit represented by general formula (5) and / or general formula (6), and a structural unit represented by formula (10), and optionally further containing a structural unit represented by general formula (MA).

[0131] In step (II), 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, and then react the resulting reaction mixture with the monofunctional (meth)acrylic compound.

[0132] (Method for producing polymer P according to the fourth embodiment) The polymer P of the fourth embodiment, which includes the structural unit represented by formula (5) and / or the structural unit represented by formula (6), and the structural unit represented by formula (8) and / or the structural unit represented by formula (9), Step (I): A step of preparing a raw material polymer containing a structural unit represented by general formula (ST), a structural unit represented by general formula (MA), and the aforementioned organic group (i) having 1 to 6 valent carbon atoms with 1 to 30 carbon atoms. Step (II): A step of reacting the raw material polymer obtained in Step (I) with 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") in the presence of a basic catalyst to prepare a polymer precursor containing a structural unit represented by general formula (ST), the aforementioned organic group (i) having 1 to 6 valent carbon atoms with 1 to 30 carbon atoms, a structural unit represented by general formula (5) and / or a structural unit represented by general formula (6), and optionally a structural unit represented by general formula (MA), and Step (IIIb): The polymer can be produced by reacting the polymer precursor obtained in Step (II) with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to prepare a polymer P containing a structural unit represented by general formula (ST), the 1-6 valent organic group (i) having 1 to 30 carbon atoms, a structural unit represented by general formula (5) and / or a structural unit represented by general formula (6), a structural unit represented by general formula (7) and / or a structural unit represented by general formula (8), and optionally a structural unit represented by general formula (MA).

[0133] In step (II), 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, and then react the monofunctional (meth)acrylic compound with the obtained reaction mixture.

[0134] Hereinafter, each step will be described. (Step (I)) The step of preparing a raw material polymer containing a structural unit represented by the general formula (ST), a structural unit represented by the general formula (MA), and the organic group (i) having 1 to 6 valences and 1 to 30 carbon atoms in step (I) can be carried out by polymerizing (addition polymerization) a monomer composition containing a styrene monomer represented by the general formula (STm) and maleic anhydride in the presence of the thiol group-containing compound having two or more functional groups. In addition, the definitions of R 1 , R 2 , and R 3 are the same as those of the general formula (ST). The same applies to the preferred embodiments.

[0135]

Chemical formula

[0136] The monomer composition may contain other monomers in addition to the above monomer. The other monomers are not particularly limited as long as they are copolymerizable compounds having a double bond, and examples include substituted or unsubstituted norbornene, maleimide, indene, acenaphthylene, norbornadiene, dihydrofuran, terpene compounds (e.g., pinene, limonene, etc.), linear alkenes (e.g., pentene, etc.), cyclic alkenes (e.g., cyclohexene, etc.), cyclododecatriene, tricycloundecane, dialkyl fumarates (e.g., dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth)acrylic acid compounds (e.g., methyl methacrylate, methyl acrylate), vinyl acetate, vinyl ethers (e.g., 2-hydroxyethyl vinyl ether, etc.). In step (I), the monomer represented by general formula (STm), maleic anhydride, and other monomers as needed can be polymerized (addition polymerized) in the presence of the thiol group-containing compound with two or more functionalities.

[0137] Examples of thiol group-containing compounds with two or more functions include, but are not limited to, the compounds represented by the chemical formulas (s-1) to (s-21) above. A single thiol group-containing compound with two or more functions may be used, or two or more may be used in combination.

[0138] 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(cyclohexanecarbonitrine) (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 the polymerization initiator, only one kind may be used, or two or more kinds may be used in combination.

[0139] As the solvent used in the polymerization reaction, for example, organic solvents such as diethyl ether, tetrahydrofuran, toluene, and methyl ethyl ketone can be used. The polymerization solvent may be a single solvent or a mixed solvent.

[0140] The synthesis of the raw material polymer is carried out by dissolving the monomer represented by the formula (STm), maleic anhydride, and a polymerization initiator in a solvent, charging them into a reaction vessel, and then heating to allow addition polymerization to proceed while dropping the thiol group-containing compound having two or more functional groups. The heating temperature is, for example, 50 to 80 °C, and the heating time is, for example, 5 to 20 hours. When charging into the reaction vessel, the molar ratio of the monomer represented by the formula (STm) to maleic anhydride is preferably 0.5:1 to 1:0.5. From the perspective of molecular structure control, the molar ratio is preferably 1:1. Also, from the perspective of controlling the content of thioether groups in the raw material polymer and the molecular weight of the raw material polymer, the charged amount of the thiol group-containing compound having two or more functional groups is preferably 0.5 to 10 mol%, particularly preferably 1 to 8 mol%, and even more preferably 2 to 6 mol% with respect to the total molar amount of the monomer represented by the formula (STm) and maleic anhydride charged into the reaction vessel. Through such a process, the "raw material polymer" can be obtained. The raw material polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, etc. Typically, it is a random copolymer or an alternating copolymer. In general, maleic anhydride is known as a monomer with strong alternating copolymerization ability.

[0141] After the synthesis of the raw material polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be carried out. Specifically, the organic phase containing the synthesized raw material polymer and the low molecular weight component is concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. Then, this solution is mixed with a poor solvent such as methanol to precipitate the monomer. By filtering and drying this precipitate, the purity of the raw material polymer can be increased.

[0142] (Step (II)) The raw material polymer obtained in Step (I) is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst, so that a part of the structural unit represented by the formula (MA) contained in the raw material polymer undergoes ring opening, and the structural unit represented by the formula (5) and / or the structural unit represented by the formula (6) are formed, and a polymer P containing the structural unit represented by the general formula (ST), the organic group (i) having 1 to 6 valences and 1 to 30 carbon atoms, and the structural unit represented by the general formula (5) and / or the structural unit represented by the general formula (6), and optionally containing the structural unit represented by the formula (MA) is obtained.

[0143] More specifically, first, a solution in which the raw material polymer is dissolved in an appropriate organic solvent is prepared. As the organic solvent, single solvents 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 it is not limited to these, and various organic solvents used in the synthesis of organic compounds and polymers can be used.

[0144] To obtain polymer P containing both the structural unit represented by general formula (ST) and the structural unit represented by general formula (5), a polyfunctional (meth)acrylic compound is added to the above solution. A basic catalyst is then added. The solution is then appropriately mixed to obtain a homogeneous solution, which contains a polymer in which at least the structural unit of general formula (ST) and the structural unit of general formula (5) are bonded to the organic group (i) having 1 to 30 carbon atoms via 1 to 6 thioether groups (step (II-i)).

[0145] 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). The definitions and specific embodiments of k, R, X1, X1', and X2 in formula (1b-m) are the same as those in formula (1b) described above. Also, in formula (1c-m), k, R, X 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.

[0146] [ka]

[0147] [ka]

[0148] [ka]

[0149] Next, the polymer obtained in step (II-i) is reacted with a monofunctional (meth)acrylic compound in the presence of a basic catalyst to obtain a polymer containing a structure in which at least the structural unit of general formula (ST), the structural unit of general formula (5), and the structural unit of general formula (6) are bonded to the organic group (i) having 1 to 30 carbon atoms via 1 to 6 thioether groups (step (II-ii)).

[0150] 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.

[0151] 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 general formula (MA) and formation of the structural unit of general formula (5) are achieved in the raw material polymer.

[0152] Furthermore, for example, by adding a monofunctional (meth)acrylic compound having a hydroxyl group to the reaction system during the heating process described above, the structural unit represented by the aforementioned general formula (6) can be introduced into the polymer P.

[0153] 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 introducing the structural unit represented by the general formula (6) into polymer P, 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 general formula (2a-m). In the general formula (2a-m), X 10 and the definitions of R are the same as those in the general formula (2a).

[0154] [Chemical formula]

[0155] Specific examples of the compound represented by the general 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.

[0156] When obtaining a polymer containing the structural unit represented by the formula (ST), the organic group (i) having 1 to 6 valences and 1 or more and 30 or less carbon atoms, and either one of the structural unit represented by the formula (1) and the structural unit represented by the formula (2), only one of the steps (II-i) and (II-ii) may be carried out after the step (I). (Step (IIIa)) When carrying out step (IIIa), a step of treating the polymer obtained in step (II) with water in the presence of a basic catalyst is used. By step (IIIa), the structural unit represented by general formula (MA) contained in the polymer obtained in step (II) undergoes ring-opening, and a structural unit represented by general formula (10) is formed, thereby producing a polymer P containing a structural unit represented by general formula (ST), a structural unit represented by general formula (5) and / or a structural unit represented by general formula (6), and a structural unit represented by general formula (10). When a part of the structural unit represented by general formula (MA) undergoes ring-opening and a part of the structural unit of general formula (MA) remains without undergoing ring-opening, polymer P contains, in addition to the structural unit represented by general formula (ST), the structural unit of general formula (5) and / or the structural unit of general formula (6), the organic group (i) having 1 to 6 valences and 1 to 30 carbon atoms, and the structural unit of general formula (310), a structural unit represented by general formula (MA).

[0157] Examples of the basic catalyst used in step (IIIa) include amine compounds or nitrogen-containing heterocyclic compounds such as triethylamine, pyridine, and dimethylaminopyridine.

[0158] In step (IIIa), water is added to the reaction system containing the polymer precursor obtained in step (II), and the resulting reaction solution is heated, preferably at 60 to 80 °C for about 0.25 to 6 hours, whereby the structural unit of formula (MA) contained in this polymer undergoes ring-opening and a structural unit represented by formula (10) is generated. The basic catalyst can be used as it is the catalyst remaining in the reaction system obtained in step (II). Therefore, step (IIIa) is preferably carried out by adding water to this reaction mixture in situ without performing any post-treatment on the reaction mixture obtained in step (II).

[0159] The polymer P of this embodiment can be obtained by the above steps. However, from the perspective of the effects of the present invention, the following steps can also be appropriately carried out as needed for removing unnecessary components other than the desired polymer.

[0160] 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.

[0161] The resulting organic solution containing polymer P is purified using either a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the organic solution of polymer P 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 is added to the obtained organic solution of polymer P, and the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This mixture is then allowed to stand for at least 30 minutes to separate the organic phase from the aqueous phase, and the aqueous phase is removed. Water is then added to the organic solution of the polymer after the removal of the aqueous phase, and the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This mixture is then 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 and removing the aqueous phase may be repeated. The obtained polymer organic solution can be concentrated by heating it under reduced pressure using a rotary evaporator, and then diluted by adding a final solvent (such as PGMEA). This process is repeated to obtain a polymer P solution dissolved in the final solvent.

[0162] Furthermore, the polymer solution may also contain the polyfunctional (meth)acrylic compound and / or monofunctional (meth)acrylic compound used in the synthesis of polymer P. 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 5 to 50%, particularly 10 to 35%, of the peak area of ​​polymer P, and the peak area derived from the monofunctional (meth)acrylic compound is 5 to 50%, particularly 10 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.

[0163] (Process (IIIb)) In step (IIIa), the polymer precursor obtained in step (II) is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst. The reaction between the carboxyl group of the polymer precursor and the epoxy group of the epoxy group-containing (meth)acrylic compound forms structural units represented by general formula (8) and / or general formula (9), thereby producing a polymer P containing a structural unit represented by general formula (ST), the 1-6 valent organic group (i) having 1 to 30 carbon atoms, a structural unit represented by general formula (5) and / or general formula (6), and a structural unit represented by general formula (8) and / or general formula (9), and optionally a structural unit represented by general formula (MA).

[0164] Step (IIIb) is preferably carried out by adding an epoxy group-containing (meth)acrylic compound to the reaction system containing the polymer precursor obtained in step (II).

[0165] The reaction between the polymer precursor and the epoxy group-containing (meth)acrylic compound proceeds in the presence of a basic catalyst. The basic catalyst can be the one remaining in the reaction system obtained in step (II). Therefore, it is preferable to carry out step (IIIb) by adding the epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor obtained in step (II) in situ, without isolating and purifying the polymer precursor from the reaction mixture containing the polymer precursor obtained in step (II) or neutralizing the basic catalyst contained in the mixture.

[0166] 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 (the carboxyl groups in formula (5) and / or formula (6)) and the epoxy groups of the epoxy group-containing (meth)acrylic compound forms structural units represented by general formula (8) and / or general formula (9), thereby generating polymer P.

[0167] 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.

[0168] 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.

[0169] After step (IIIb), it is preferable to perform the following steps as appropriate to remove unwanted components other than the desired polymer P.

[0170] First, the reaction solution, which has been diluted with an organic solvent and to which an acid (e.g., formic acid, citric acid, etc.) has been added, is vigorously stirred in a separatory funnel for at least 3 minutes. This is then 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 polymer P is obtained.

[0171] An excess amount of toluene is added to the organic solution of polymer P obtained to reprecipitate polymer P. The polymer powder obtained by reprecipitation is then washed with toluene several more times (for example, twice). Furthermore, to remove acidic and basic catalysts, the obtained polymer powder is washed with deionized water several times (for example, three times). High-purity polymer (A) of this embodiment can be obtained by drying the polymer powder after washing with deionized water at, for example, 30-60°C for 16 hours or more.

[0172] [Polymer solution] The polymer solution of this embodiment contains the polymer P described above. The polymer solution of this embodiment may contain, along with polymer (A), at least one selected from polyfunctional (meth)acrylic compounds, monofunctional (meth)acrylic compounds, and compounds having a thiol group and an alkoxy group or their oligomers.

[0173] (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 the production of polymer P, or may be added separately.

[0174] 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 general formulas (1b-p), (1c-p), and (1d-p).

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] k, R, and X in the general formula (1b-p) 1 , X 1 'and X 2 The definition and specific form of are the same as those in general formula (1b) above. Also, k, R, and X in general formula (1c-p) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific form of are the same as those in the general formula (1c) described above.

[0179] In general formulas (1b-p), (1c-p), and (1d-p), Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0180] Compounds in which Y is a hydrogen atom in general formulas (1b-p), (1c-p), and (1d-p) may be unreacted monomers (i.e., compounds represented by general formulas (1b-p), (1c-p), and (1d-p)) and may be added separately. In the general formula (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.

[0181] 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, the amount added can be such that the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less, relative to the peak area of ​​polymer P.

[0182] (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).

[0183] [ka]

[0184] 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, the amount added can be such that the peak area derived from the monofunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less, relative to the peak area of ​​polymer P.

[0185] (A compound having a thiol group and an alkoxy group, or its oligomer (Compound (B))) The compound having a thiol group and an alkoxy group or its oligomer (hereinafter referred to as "compound (B)") that can be incorporated into the polymer solution of this embodiment can be any known compound that has a thiol group and an alkoxy group, as long as it exhibits the effects of the present invention.

[0186] The polymer solution of this embodiment, by containing compound (B) or its oligomer, can provide a resin cured product with excellent adhesion to a substrate or the like. The substrate is not particularly limited, but as will be described later, examples include glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, copper-clad laminates, and the like.

[0187] In this embodiment, the alkoxy group contained in compound (B) is preferably a carbon-1 to carbon-3 alkoxy group from the viewpoint of the effects of the present invention, and it is also preferable that the compound has a structure in which a thiol group and an alkoxy group are bonded to an organic chain which may contain one or more atoms selected from O, N, S, P and Si. Specifically, compound (B) preferably contains a compound represented by the following general formula (a).

[0188] [ka]

[0189] In general formula (a), each R independently represents an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and at least two of the Rs are alkoxy groups having 1 to 3 carbon atoms. L represents an m+n valent organic chain which may contain one or more atoms selected from O, N, S, P, and Si.

[0190] In this embodiment, examples of m+n valent organic chains of L include linear or branched alkylene groups having 1 to 10 carbon atoms (m+n:2), m+n valent groups derived from linear or branched alkanes having 1 to 20 carbon atoms, and m+n valent groups derived from substituted or unsubstituted siloxanes.

[0191] X represents a single bond or a divalent organic group which may contain a carbonyl group, a (thio)ester group, or a (thio)amide group. In this embodiment, X is preferably a single bond or an alkylene ester group having 1 to 10 carbon atoms. Q represents a single bond or a divalent organic group which may contain a carbonyl group, a (thio)ester group, or a (thio)amide group. In this embodiment, Q is preferably a single bond or an alkylene ester group having 1 to 10 carbon atoms. The molar ratio (m:n) is between 1:1 and 1:8, and m+n is between 2 and 20. The weight-average molecular weight of the compound is between 100 and 2000.

[0192] Examples of compound (B) include 3-mercaptopropylmethyldimethoxysilane (KBM-802, manufactured by Shin-Etsu Silicone Co., Ltd.), 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Silicone Co., Ltd.), (3-mercaptopropyl)triethoxysilane, siloxane chain-containing polyfunctional silane coupling agent (KR-519, manufactured by Shin-Etsu Silicone Co., Ltd.), and organic chain-containing polyfunctional silane coupling agent having the following structural units.

[0193] [ka]

[0194] In the general formula above, the molar ratio a:b is 2:1 to 4:1. The weight-average molecular weight is 1000 to 1500. * indicates a bond. Examples of such compounds include X-12-1154 (manufactured by Shin-Etsu Silicone Co., Ltd.). Furthermore, compound (B) or its oligomer may be used alone or as a mixture of two or more types.

[0195] In the polymer solution of this embodiment, compound (B) is blended in an amount of 0.25 to 20% by mass, preferably 1.0 to 15% by mass, and more preferably 2.0 to 12% by mass, relative to the polymer P, from the viewpoint of the effects of the present invention.

[0196] 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.

[0197] 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.

[0198] [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.

[0199] [Photosensitive resin composition] The photosensitive resin composition of this embodiment comprises the polymer P described above 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.

[0200] (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.

[0201] 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.

[0202] (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.

[0203] 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.

[0204] 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.).

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] (Surfactants) The photosensitive resin composition of this embodiment may contain a surfactant, and a nonionic surfactant is preferred as the surfactant.

[0210] 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.

[0211] 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.

[0212] (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.

[0213] 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.

[0214] (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.

[0215] 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.

[0216] (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 the polymer (being able to chemically bond with the polymer) 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.

[0217] 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.

[0218] 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:

[0219] 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.

[0220] 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.

[0221] (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.

[0222] [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.

[0223] (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.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] (exposure) Exposure is typically performed by irradiating a photosensitive resin film with active light through a suitable photomask.

[0229] 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.

[0230] 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.

[0231] (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.

[0232] 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.

[0233] 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.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] 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, which includes a color filter and / or black matrix.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. Examples of embodiments are provided below.

[0242] [1] A monomer composition comprising a monomer represented by formula (STm) and maleic anhydride is polymerized in the presence of a thiol group-containing compound with two or more functionalities to prepare a raw material polymer; A method for producing a polymer, comprising the step of reacting the aforementioned raw material polymer with a polyfunctional (meth)acrylic compound and / or a monofunctional methacrylic compound in the presence of a basic catalyst to obtain a polymer. [ka] (In equation (STm), R 1 , R 2 , and R 3 Each of these is independently either a hydrogen atom or an organic group with 1 to 30 carbon atoms.

[0243] [2] A process to prepare a raw material polymer by polymerizing a monomer composition containing a monomer represented by formula (STm) and maleic anhydride in the presence of a thiol group-containing compound with two or more functionalities, The process involves reacting the aforementioned raw material polymer with a polyfunctional (meth)acrylic compound and / or a monofunctional methacrylic compound 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 equation (STm), R 1 , R 2 , and R 3 Each of these is independently either a hydrogen atom or an organic group with 1 to 30 carbon atoms.

[0244] [3] A process to prepare a raw material polymer by polymerizing a monomer composition containing a monomer represented by formula (STm) and maleic anhydride in the presence of a thiol group-containing compound with two or more functionalities, The process involves reacting the aforementioned raw material polymer with a polyfunctional (meth)acrylic compound and / or a monofunctional methacrylic compound in the presence of a basic catalyst to prepare a polymer precursor. A method for producing a polymer, comprising the step of reacting the aforementioned polymer precursor with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to obtain a polymer. [ka] (In equation (STm), R 1 , R 2 , and R 3 Each of these is independently either a hydrogen atom or an organic group with 1 to 30 carbon atoms.

[0245] [4] A method for producing a polymer according to any one of [1] to [3], wherein the thiol group-containing compound with two or more functions is at least one compound selected from formulas (s-1) to (s-21). [ka]

[0246] [4] A polymer solution comprising a polymer obtained by a polymer manufacturing method described in any of [1] to [3].

[0247] [5] The polymer solution according to [4], further comprising at least one selected from polyfunctional (meth)acrylic compounds, monofunctional (meth)acrylic compounds, and compounds having a thiol group and an alkoxy group or their oligomers.

[0248] [6] A polymer solution according to [4] or [5] used for forming a color filter or black matrix.

[0249] A photosensitive resin composition comprising a polymer solution as described in [7] [4] or [5] and a photopolymerization initiator.

[0250] [8] [7] Cured product of the photosensitive resin composition described above. [Examples]

[0251] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0252] The compounds used in the examples may be indicated by the following abbreviations or trade names. • MA: Maleic anhydride St: Styrene Vt: Vinyltoluene (4-methylstyrene) • MEK: Methyl ethyl ketone • PEMP: Pentaerythritol tetrakis(3-mercaptopropionate), a thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemicals Co., Ltd.) NB:2-Norbornen 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.).

[0253] [ka]

[0254] GMA: Glycidyl methacrylate • KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.)

[0255] <Synthesis of raw material polymers> (Preparation of raw material polymer 1) XIRAN® 1000 (manufactured by Tomoe Engineering Co., Ltd., styrene-maleic anhydride copolymer, (styrene:maleic acid ratio = 1:1)), a copolymer consisting of styrene-derived structural units and maleic anhydride-derived structural units, was prepared and used as raw material polymer 1. The weight-average molecular weight Mw of raw material polymer 1 was 6478, and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.51.

[0256] (Synthesis of raw material polymer 2) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 122.40 g (1.18 mol) of styrene (St), 115.24 g (1.18 mol) of maleic anhydride (MA), and 1940.42 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, 10.82 g, 0.047 mol) and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP, 22.97 g, 0.047 mol) dissolved in 164.49 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 237.1 g of a polymer (raw material polymer 2) comprising 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 14633, with a polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) of 5.11.

[0257] [Structural analysis of raw material polymer 2] The synthesis of raw material polymer 2 begins with the monomer and PEMP dissolved in the solvent at the start of the reaction, after which the reaction proceeds to produce the polymer. Analysis of the reaction solution and the resulting polymer yielded the following results.

[0258] (a) Analysis of the reaction solution GPC analysis of the reaction solution before reprecipitation and purification showed no peak for PEMP alone. This confirmed that no PEMP remained in the reaction solution. Furthermore, GC (gas chromatography) analysis of the reaction solution before reprecipitation and purification showed a decrease in the peaks for styrene and maleic anhydride alone in the reaction solution after the reaction compared to before the reaction, confirming that styrene and maleic anhydride reacted to form a polymer. The measurement conditions for gas chromatography were 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.

[0259] (b) Analysis of polymers GPC analysis of the polymer after reprecipitation and purification did not reveal peaks for PEMP, styrene, or maleic anhydride. This confirmed that no PEMP, styrene, or maleic anhydride remained in the polymer. The amount of sulfur in the obtained raw material polymer 2 was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in raw material polymer 2. Furthermore, GPC measurement of the reaction solution did not show a peak for PEMP alone, indicating that no unreacted PEMP remained, thus confirming that PEMP was incorporated into raw material polymer 2.

[0260] The elemental analysis method is as follows: - Test items Flask combustion and ion chromatography for the determination of total sulfur. - Test method Flask combustion ~ Ion chromatography (1) Completely combust approximately 50 mg of the sample in a sealed flask with oxygen replaced. (2) The generated gas is collected in the hydrogen peroxide absorption solution that has been added to the flask beforehand, and the volume is adjusted to 50 ml to be used as the test solution. (3) The sample solution and standard solution are introduced into an ion chromatograph, and the concentration of sulfate ions is determined by the calibration curve method to calculate the amount of sulfur contained in the sample. -Equipment used DIONEX ICS-3000 Ion Chromatograph

[0261] [Confirmation of the thioether structure contained in raw material polymer 2] 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.

[0262] [ka]

[0263] Raw material polymer 2 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 starting polymer 2.

[0264] Also, raw material polymer 2 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 raw material polymer 2 possesses a skeleton with a thioether group as shown below, and the thiol group has disappeared. The polymers of the examples synthesized using raw material polymer 2 are thought to possess a similar skeleton.

[0265] [ka]

[0266] 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)

[0267] 13 Based on 1C-NMR measurements, the amount of PEMP incorporated into raw material polymer 2 was calculated to be 1.7 mol% relative to the total amount of styrene and maleic anhydride in raw material polymer 2, using the following calculation method.

[0268] [Method for calculating the amount (mol%) of PEMP in raw material polymer 2] First, the amount of PEMP introduced into the raw polymer 2 is calculated from the peak integral value of 60 ppm-64 ppm, which corresponds to peak b (4C) of PEMP. Next, by subtracting the peak integral value corresponding to the PEMP peak bd (4C) that overlaps with the 170ppm-175ppm peak integral value (the integral value of PEMP peak b = the integral value of PEMP peak d), the amount of MA in raw material polymer 2 corresponding to the maleic anhydride (MA) peak e (2C) below is calculated.

[0269] [ka]

[0270] Then, the amount of ST in raw polymer 2 is calculated from the peak integral values ​​of 125 ppm-142 ppm, which correspond to the aromatic ring (6C portion) of styrene (ST). Based on the above, the amount of PEMP incorporated into raw material polymer 2 (mol%) relative to the total amount of styrene and maleic anhydride in raw material polymer 2 is calculated as "(amount of PEMP in raw material polymer 2) ÷ ((amount of MA in raw material polymer 2) + (amount of ST in raw material polymer 2))".

[0271] (Synthesis of raw material polymer 3) 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 4) comprising structural units derived from 2-norbornene 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 3500, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.62. [Confirmation of the thioether structure contained in raw material polymer 3] Raw material polymer 3 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 3.

[0272] Also, raw material polymer 3 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 3 possesses a skeleton with a thioether group as shown below, and the thiol group has disappeared. The comparative polymer synthesized using raw material polymer 3 is also thought to possess a similar skeleton.

[0273] [ka]

[0274] 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 polymer.

[0275] Elemental analysis revealed that the sulfur content in raw polymer 3 was 2.4 wt%.

[0276] (Synthesis of raw material polymer 4) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 138.89 g (1.18 mol) of vinyltoluene (VT), 115.24 g (1.18 mol) of maleic anhydride (MA), and 1940.42 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. When the internal temperature reached 80°C, a solution of 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, trade name: V-601, 10.82 g, 0.047 mol) and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP, 22.97 g, 0.047 mol) dissolved in 164.49 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 245.15 g of a polymer (raw material polymer 4) comprising structural units derived from vinyltoluene 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 26618, with a polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) of 3.27.

[0277] [Structural analysis of raw material polymer 2] The synthesis of raw material polymer 2 begins with the monomer and PEMP dissolved in the solvent at the start of the reaction, after which the reaction proceeds to produce the polymer. Analysis of the reaction solution and the resulting polymer yielded the following results.

[0278] (a) Analysis of the reaction solution GPC analysis of the reaction solution before reprecipitation and purification showed no peak for PEMP alone. This confirmed that no PEMP remained in the reaction solution. Furthermore, GC (gas chromatography) analysis of the reaction solution before reprecipitation and purification showed a decrease in the peaks for styrene and maleic anhydride alone in the reaction solution after the reaction compared to before the reaction, confirming that vinyltoluene and maleic anhydride reacted to form a polymer.

[0279] (b) Analysis of polymers GPC analysis of the polymer after reprecipitation and purification did not reveal peaks for PEMP, vinyltoluene, or maleic anhydride. This confirmed that no PEMP, vinyltoluene, or maleic anhydride remained in the polymer. The amount of sulfur in the obtained raw material polymer 4 was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the raw material polymer 4. Furthermore, GPC measurement of the reaction solution did not show a peak for PEMP alone, indicating that no unreacted PEMP remained, thus confirming that PEMP was incorporated into the raw material polymer 4.

[0280] <Preparation of Polymer P (polymer solution)> Polymer P was prepared in each preparation example. Table 1 shows the components used in each preparation example, the amount of each component charged in terms of maleic anhydride (MA), and the amount of each structural unit (mole fraction, mol%). 1 The values ​​were calculated by integral analysis of H-NMR and are shown in terms of maleic anhydride (MA).

[0281] (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 (0.049 mol in MA equivalent) of the raw material polymer to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to this solution, followed by 3.00 g (0.030 mol) of triethylamine, and 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 with an excess amount of water, and this process was repeated twice. The resulting reaction product was dried at 40°C for 12 hours. Based on the above, 8.0 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 1. 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.

[0282] (Preparation Example 2) Except for replacing raw material polymer 1 in Preparation Example 1 with raw material polymer 2, the same procedure was followed to obtain 7.5 g of polymer P2, in which the structural units derived from maleic anhydride in raw material polymer 2 were ring-opened with 4-HBA. 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 1. Furthermore, GPC analysis of polymer P2 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P2 did not contain any unreacted monofunctional (meth)acrylic compound.

[0283] (Preparation Example 3) A resin mixture containing polymer P3, which was obtained by ring-opening the MA units of raw material polymer 1 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 99.71 g of MEK to 60.00 g (0.297 mol in MA equivalent) of the raw material polymer 1. 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 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 the aqueous phase was removed from the reaction solution by treating it with aqueous formic acid solution and aqueous citric acid solution. 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 solvent was removed from the resulting reaction mixture under reduced pressure at 50°C using a rotary evaporator. The solvent removal operation was stopped when the solid content concentration of the polymer solution was confirmed to be 27±2 mass% by measurement using a heat-drying type moisture meter. Then, PGMEA was added to bring the solid content concentration to 18 mass% and mixed until homogeneous. The same procedure was repeated two more times, removing the solvent under reduced pressure at 50°C, adjusting the solid content concentration to 27±2 mass% by measurement using a heat-drying type moisture meter, and then adding PGMEA to bring the solid content concentration to 18 mass% and mixing until homogeneous. After that, the solvent was removed or PGMEA was added and stirred until homogeneous to bring the solid content concentration to 30±3 mass%. Through these operations, the solvent used in the reaction was removed and replaced with PGMEA. Based on the above, polymer P3 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 1 with A-TMM-3LM-N, 4-HBA, and water, and polymer solution 3 containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained. The obtained polymer solution 3 was analyzed by gel permeation chromatography to determine the amounts of polymer P3, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the composition, as well as the weight-average molecular weight and polydispersity of polymer P3. The results are shown in Table 1. 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 P3 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 P3: Peak detected before 20 minutes (a peak with a shorter retention time and larger molecular weight than A-TMM-3LM-N and 4-HBA) -A-TMM-3LM-N: sum 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).

[0284] (Preparation Example 4) Except for changing raw material polymer 1 to raw material polymer 2 in preparation example 3, the procedure is the same as in preparation example 3. Polymer P4 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 2 with A-TMM-3LM-N, 4-HBA, and water, and polymer solution 4 containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained. The obtained polymer solution 4 was analyzed by gel permeation chromatography to determine the amounts of polymer P4, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the composition, as well as the weight-average molecular weight and polydispersity of polymer P4. The results are shown in Table 1. 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 P4 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 P4: Peak detected before 20 minutes (a peak with a shorter retention time and larger molecular weight than A-TMM-3LM-N and 4-HBA) -A-TMM-3LM-N: sum 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).

[0285] (Preparation Example 5) Polymer solution 5 was prepared by mixing the additives listed in Table 1 with the polymer solution 4 obtained in Preparation Example 4, in the amounts indicated in "Additive Amount" in Table 1. Here, the amount of additive was mixed in weight percent relative to the solid content (polymer P4, polyfunctional (meth)acrylic compound, monofunctional (meth)acrylic compound) in polymer solution 4.

[0286] (Preparation Example 6) Polymer P6 was prepared by ring-opening the MA units of raw material polymer 1 with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), and then reacting them with an epoxy group-containing (meth)acrylic compound (GMA). The details are described below. First, a solution was prepared by adding 102.63 g of MEK to 60 g of the raw polymer (0.297 mol in MA equivalent). Next, 58.12 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the reaction was carried out at 70°C for 2 hours. Subsequently, 27.01 g (0.187 mol) of 4-HBA was added, and the reaction was carried out at 70°C for 4 hours. Finally, 13.31 g (0.094 mol) of GMA was added, and the reaction was carried out at 70°C for 4 hours to prepare the 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 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 16 hours. Based on the above, 44.2 g of polymer P6 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 1 with A-TMM-3LM-N and 4-HBA, and reacting them with GMA.

[0287] GPC analysis of polymer P6 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic compound, monofunctional (meth)acrylic compound, and epoxy group-containing (meth)acrylic compound used. This confirmed that the obtained polymer P6 did not contain unreacted (meth)acrylic compounds, (meth)acrylic compounds without hydroxyl groups, or unreacted epoxy group-containing (meth)acrylic compounds.

[0288] (Preparation Example 7) Except for replacing raw material polymer 1 with raw material polymer 2 in Preparation Example 6, the same procedure was followed, and 35.0 g of polymer P7 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 2 with A-TMM-3LM-N and 4-HBA, and reacting them with GMA.

[0289] GPC analysis of polymer P7 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic compound, monofunctional (meth)acrylic compound, and epoxy group-containing (meth)acrylic compound used. This confirmed that the obtained polymer P7 did not contain unreacted (meth)acrylic compounds, (meth)acrylic compounds without hydroxyl groups, or unreacted epoxy group-containing (meth)acrylic compounds.

[0290] (Preparation Example 8) Except for replacing raw material polymer 1 with raw material polymer 3 in Preparation Example 1, the procedure was the same as in Preparation Example 1, and 8.7 g of polymer P8 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 3 with 4-HBA. The obtained polymer P8 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 1. Furthermore, GPC analysis of polymer P8 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P8 did not contain any unreacted monofunctional (meth)acrylic compound.

[0291] (Preparation Example 9) (Polymer synthesis) Polymer P9 was prepared by ring-opening the MA units of raw material polymer 3 with a monofunctional (meth)acrylic compound (HEMA), and then reacting it with an epoxy group-containing (meth)acrylic compound (GMA). The details are described below. First, a solution was prepared by adding 111.43 g of MEK to 60 g of raw polymer 3 (0.312 mol in MA equivalent). Next, 25.38 g (0.195 mol) of HEMA was added to this solution, followed by 6.00 g (0.059 mol) of triethylamine, and the mixture was reacted at 70°C for 6 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 the 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 following procedure. • The polymer was reprecipitated 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 16 hours. Based on the above, 35.1 g of polymer P9 was obtained by ring-opening the structural units derived from maleic anhydride in the raw material polymer with HEMA and reacting them with GMA. GPC analysis of polymer P9 confirmed the disappearance of the peaks of the monofunctional (meth)acrylic compound and the epoxy group-containing (meth)acrylic compound used. This confirmed that the obtained polymer P9 did not contain any unreacted (meth)acrylic compounds or epoxy group-containing (meth)acrylic compounds.

[0292] (Preparation Example 10) (Polymer synthesis) A polymer P10 was obtained by ring-opening the MA units of the raw material polymer 4 with A-TMM-3LM-N, 4-HBA, and water, and a polymer solution 6 containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained. First, a solution was prepared by adding 99.71 g of MEK to 60.00 g (0.277 mol in MA equivalent) of the raw material polymer 4. 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 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 reaction was carried out 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 treatment with aqueous formic acid solution and aqueous citric acid solution. Furthermore, liquid-liquid extraction and subsequent solvent replacement were performed in the same manner as in Preparation Example 3. The obtained polymer solution 6 was analyzed by gel permeation chromatography to determine the amounts of polymer P10, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the composition, as well as the weight-average molecular weight and polydispersity of polymer P10. The results are shown in Table 1. 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 P4 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 P10: Peak detected before 20 minutes (a peak with a shorter retention time and larger molecular weight than A-TMM-3LM-N and 4-HBA) -A-TMM-3LM-N: sum 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).

[0293] (Preparation Example 11) Polymer P11 was prepared by ring-opening the MA units of raw material polymer 2 with trifunctional (meth)acrylic compounds, monofunctional (meth)acrylic compounds, and water. Details are described below. First, a solution was prepared by adding 99.71 g of MEK to 60.00 g (0.297 mol in MA equivalent) of the raw material polymer 2. 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 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 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 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 16 hours. Based on the above, 31.0 g of polymer P11 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 2 with A-TMM-3LM-N, 4-HBA, and plenty of water. GPC analysis of polymer P11 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the resulting polymer P11 did not contain any unreacted (meth)acrylic compounds or (meth)acrylic compounds without hydroxyl groups.

[0294] (Evaluation of physical properties) The acid value and double bond equivalent of polymer P synthesized in the examples and comparative examples were measured by the method described below.

[0295] (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. 1The 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 1. An acid value of 70 gKOH / g or higher indicates that the polymer contains sufficient carboxyl groups necessary for adequate development.

[0296] (double bond equivalent) The double bond equivalents of the polymer were measured by the following method. Similar to the above method for measuring acid value, 1 ¹H-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 1. A smaller double bond equivalent value indicates a larger amount of C=C double bonds per unit mass of polymer.

[0297] [Table 1]

[0298] (Examples 1-6, Comparative Examples 1-5) In each example and comparative example, the following items were evaluated. <Rating> [Alkaline dissolution rate of polymer solutions] Polymers P1, P2, P6-9, and P11 obtained in Preparation Examples 1, 2, 6-9, and 11 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid content of 30% by mass. Next, the above solution or polymer solutions 3-6 obtained in Preparation Examples 3-5 and 10 were spin-coated onto the wafer, the PGMEA was dried, and then a resin film with a thickness of approximately 2 μm was fabricated by pre-baking at a temperature of 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 2. If the alkali dissolution rate is 200 nm / s or higher, it can be used without problems as a photosensitive material. If it is 500 nm / s or higher, it can be considered good, if it is 800 nm / s or higher, the developability can be considered particularly good, and if it is 1000 nm / s or higher, the developability can be considered even better.

[0299] [Sensitivity evaluation of photosensitive resin composition 1 (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, P2, P6-9, P11 (polymers P1, P2, P6-9, P11 from Preparation Examples 1, 2, 6-9, and 11) or polymer solutions 3-6 (polymer solutions 3-6 obtained in Preparation Examples 3-5 and 10): 100 parts by mass (Here, polymer solutions 3 to 6 were weighed so that the solid content (the total amount of polymers P3, P4, or P10 and the polyfunctional (meth)acrylic compound, and the total amount including additives if any) 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

[0300] 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 (%) = (Thickness of thin film B at each exposure dose / Thickness of thin film Af) × 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 2. The exposure dose at which a residual film rate of 90% or more was 20 mJ / cm² 2 The sensitivity is good if it is below 15 mJ / cm². 2 The following conditions indicate particularly good sensitivity.

[0301] [Sensitivity evaluation of resin composition 2 (residual film rate after exposure at low exposure dose)] (5mJ / cm 2 (Percentage of residual film at the exposure level) The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above 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 3.0 μm (±0.3 μm). This thin film A is subjected to a photomask with a light-shielding rate of 1-100% using a Canon g+h+i-ray mask aligner (PLA-501F) at a rate of 5 mJ / cm². 2 The g+h+i line was exposed with the specified exposure dose. After exposure, the thin film was developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (immersed together with the wafer) to obtain thin film B. 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

[0302] (10mJ / cm 2 (Percentage of residual film at the exposure level) The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above 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 3.0 μm (±0.3 μm). This thin film A is subjected to a 10 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 was developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (immersed together with the wafer) to obtain thin film B. 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 10 mJ / cm 2If the residual film rate at the exposure level is 50% or more, it can be used without any problems as a photosensitive material.

[0303] [Alkaline dissolution rate of photosensitive resin composition (2.0% by mass sodium carbonate aqueous solution)] The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above was spin-coated onto a wafer using the above solution, 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 that time by the film thickness. The results are shown in Table 2. 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 500 nm / s or higher, it can be considered to have particularly good developability; and if it is 900 nm / s or higher, it can be considered to have even better developability.

[0304] [Yellow Index] The photosensitive resin composition prepared in Sensitivity Evaluation 1 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 conditions 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 2. The lower the yellow index, the better the heat discoloration resistance. A value of 1.30 or less indicates that it can be used without problems as a photosensitive resin, a value of 1.20 or less indicates that it has good heat discoloration resistance, and a value of 0.90 or less indicates that it has particularly good heat discoloration resistance.

[0305] The results of the developability and sensitivity evaluations are shown in Table 2.

[0306] [Table 2]

[0307] The photosensitive resin composition of the example exhibited a good alkaline dissolution rate and, therefore, excellent developability. The photosensitive resin composition of the example required an exposure dose of 20 mJ / cm² to achieve a residual film rate of 90% or more. 2 In other words, it hardens with low exposure and has high sensitivity. Therefore, the photosensitive resin composition of the example had a good balance of high developability, high sensitivity, and a low yellow index.

[0308] <Creating a color filter> To the photosensitive resin compositions prepared in Examples 1 to 6, 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 exposure and alkaline development processes, we were able to create a green color filter. Furthermore, instead of NX-061, the company's own NX-053 (blue) and NX-032 (red) pigment dispersions were used to form blue or red color filters.

[0309] <Creation of a Black Matrix> To the photosensitive resin compositions prepared in Examples 1 to 4, 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, a black matrix could be formed. [Explanation of symbols]

[0310] 10 circuit boards 11 Black Matrix 12 Color Filters 13 Protective film 14 Transparent electrode layer

Claims

1. A polymer having the structure represented by formula (P). 【Chemistry 1】 (In equation (P), m is 0, n is an integer between 1 and 6. p is greater than 0, q is greater than 0, and r is 0. p represents the molar content of A, q represents the molar content of B, and p + q = 1. X is hydrogen, Y is an organic group having a thioether group, which is a 1-6 valent organic group derived from at least one selected from two or more thiol group-containing compounds represented by formula (s-1) to (s-21), and the organic group having the thioether group is bonded to the structural unit in [ ]n via the thioether group (*-S-* (* is a bond)) derived from the thiol group-containing compound, A represents a structural unit represented by formula (ST), B includes at least one structural unit selected from the structural units represented by formula (5), formula (6), formula (8), and formula (9), The structural units A and B are arranged randomly or alternately. 【Chemistry 2】 (In equation (ST), R １ , R ２ and R ３ Each of these is independently either a hydrogen atom or an organic group having 1 to 30 carbon atoms. 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 (In equations (5), (6), (8), and (9), R ｐ This represents a group containing two or more (meth)acryloyl groups, R ｓ This represents a group containing one (meth)acryloyl group, 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, If Q is the alkyl group and X is the alkylene group, Q and X may condense to form a cyclic group. 【Transformation 7】

2. The polymer according to claim 1, wherein B further comprises a structural unit represented by formula (10). 【Transformation 8】

3. The polymer according to claim 1 or 2, wherein B further comprises a structural unit represented by formula (MA). 【Chemistry 9】

4. R in the structural unit represented by formula (5) or (8) ｐ The polymer according to any one of claims 1 to 3, wherein the group 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 10】 (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 by -L-M- (where L is -O- or -OCO-, and M 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 ' is a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by -L'-M' - (L' is an alkylene group having 1 to 6 carbon atoms, and M' is -O- or -COO-), X ２ (This refers to a k+1 valent organic group with 1 to 12 carbon atoms.) 【Chemistry 11】 (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 It is 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 with 1 to 6 carbon atoms.) 【Chemistry 12】 (In formula (1d), n is an integer between 2 and 5. R represents a hydrogen atom or a methyl group, and multiple Rs may be the same or different.

5. R in the structural unit represented by formula (6) or (9) ｓ The polymer according to any one of claims 1 to 4, wherein the group is represented by formula (2a). 【Chemistry 13】 (In equation (2a), X １０ (where R is a divalent organic group, and R is either a hydrogen atom or a methyl group.)

6. The polymer according to any one of claims 1 to 5, wherein the weight-average molecular weight is 5,000 or more and 80,000 or less.

7. A polymer solution comprising the polymer described in any one of claims 1 to 6.

8. The polymer solution according to claim 7, further comprising at least one selected from a polyfunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and a compound having a thiol group and an alkoxy group or an oligomer thereof.

9. A polymer solution according to claim 7 or 8, used for forming a color filter or a black matrix.

10. A polymer solution according to claim 7 or 8, A photosensitive resin composition comprising a photopolymerization initiator.

11. A cured product of the photosensitive resin composition according to claim 10.

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