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

Abstract

To provide a photosensitive resin composition which has good sensitivity, has high alkali solubility, and is reduced in yellowing.SOLUTION: A polymer P has such a structure that a side chain derived from a compound having a hydroxy group and two or more (meth)acryloyl groups is introduced to a raw material polymer composed of a monofunctional or di- or higher functional thiol group-containing compound-derived structural unit, a norbornene monomer-derived structural unit, a styrene monomer-derived structural unit, and a maleic acid anhydride monomer-derived structural unit, and such a structure that a side chain derived from an epoxy group-containing (meth)acrylic compound is introduced thereto.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Liquid crystal display devices and solid-state image sensors typically include a color filter, a black matrix, spacers (e.g., photospacers, colored spacers, black spacers), and partition materials (e.g., transparent banks, black banks). The color filter, black matrix, spacers, and partition materials are configured with structures such as colored patterns and protective films formed on a substrate. Among these structures, the most common method for forming colored patterns and protective films is by photolithography using a photosensitive resin composition. Various studies have been conducted on photosensitive resin compositions. For example, Patent Document 1 describes a photosensitive resin composition comprising an alkali-soluble resin having at least one acidic group and two or more different polymerizable unsaturated groups in its side chain, a polymerizable compound, and a photopolymerization initiator. Furthermore, the examples in Patent Document 1 describe the synthesis of a methacrylic acid / allyl methacrylate / glycidyl adduct as the alkali-soluble resin, and the preparation of a photosensitive resin composition using this adduct. [Prior art documents] [Patent Documents]

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

[0004] Photosensitive resin compositions used to form color filters, black matrices, spacers, or partition materials utilize resins that undergo polymerization and harden upon exposure to light. Color filters, black matrices, spacers, or partition materials are manufactured by patterning the photosensitive resin composition through exposure and development, followed by hardening. While "increasing sensitivity" may seem like a common challenge in 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.

[0005] Furthermore, when forming color filters or black matrices, especially when the pigment content in the photosensitive resin composition is high, the low solubility of the pigment in basic developers prolongs the development time of the photosensitive resin composition. Therefore, it is necessary to use a strongly basic developer that develops faster than conventional basic developers. However, if the alkali solubility of the polymer is high, the alkali dissolution rate of the photosensitive resin composition containing pigments and photopolymerization initiators may be too fast, or the difference in dissolution rates between the pigment and the resin composition may become too large, resulting in patterns after exposure and development not conforming to the designed shape.

[0006] Furthermore, when a photosensitive resin composition is applied to a substrate or the like, and the resulting coating film is exposed to light and developed to form a pattern, excellent adhesion to the substrate or the like is required from the viewpoint of product yield and product reliability, and the cured product of the photosensitive resin composition is required to have high transparency. [Means for solving the problem]

[0007] When using a strongly basic developer, in order to obtain a pattern with a designed shape after exposure and development, it is necessary to adjust the alkali solubility of the polymer contained in the photosensitive resin composition while maintaining and improving the sensitivity, having excellent adhesion to the substrate, and further having high transparency. Furthermore, the inventors have found that this problem can be solved by improving the polymer structure, and have completed the present invention.

[0008] According to the present invention, a polymer having a structure represented by formula (P),

Chemical formula

[0009] Furthermore, according to the present invention, a polymer solution containing the above-mentioned polymer is provided.

[0010] Furthermore, the present invention provides a photosensitive resin composition comprising the above-mentioned polymer solution and a photopolymerization initiator.

[0011] Furthermore, the present invention provides a cured product of the above-mentioned photosensitive resin composition. [Effects of the Invention]

[0012] The present invention provides a photosensitive resin composition that has good sensitivity, high alkali solubility, and therefore excellent developability, as well as reduced yellowing, and a polymer for use therein. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic diagram (cross-sectional view) illustrating an example of the structure of a liquid crystal display device and / or a solid-state image sensor. [Figure 2] This is the 13C-NMR chart of raw material polymer 5. [Figure 3] This is the 1H-NMR chart of polymer P11 obtained in Preparation Example 11. [Modes for carrying out the invention]

[0014] 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".

[0015] 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.

[0016] 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.

[0017] [Polymer P] (First embodiment) In the first embodiment, the polymer of this embodiment (hereinafter referred to as "polymer P") is Step I involves polymerizing a monomer composition containing a monomer represented by the following formula (NBm), a monomer represented by the following formula (STm), and a monomer represented by the following formula (MAm) in the presence of a monofunctional or bifunctional or more thiol group-containing compound to prepare a raw material polymer. Step IIa: Reacting this raw material polymer with a compound having a hydroxyl group and two or more (meth)acryloyl groups in the presence of a basic catalyst to obtain a first polymer precursor. Step III: Reacting the first polymer precursor with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst. This polymer is obtained by [the following method].

[0018] [ka]

[0019] In the formula (NBm), R 1 , R 2 , R3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2.

[0020] [ka]

[0021] In the formula (STm), R 10 , R 11 and R 12 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R 13 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms.

[0022] [ka]

[0023] In the formula (MAm), R 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0024] The polymer P of this embodiment has a structure in which a side chain derived from a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as a "polyfunctional (meth)acrylic compound") used in step IIa above is introduced into a raw material polymer composed of structural units derived from raw material monomers used in step I above (i.e., structural units derived from monofunctional or bifunctional or more thiol group-containing compounds, structural units derived from norbornene monomer represented by formula (NBm), structural units derived from styrene monomer represented by formula (STm), and structural units derived from maleic anhydride monomer represented by formula (MAm)), and a structure in which a side chain derived from an epoxy group-containing (meth)acrylic compound used in step III above is introduced. Here, the side chain derived from the polyfunctional (meth)acrylic compound is a residue obtained by removing a hydrogen atom from the hydroxyl group of the polyfunctional (meth)acrylic compound, and is a group having two or more (meth)acryloyl groups. Furthermore, the side chain derived from the epoxy group-containing (meth)acrylic compound is a group formed when the epoxy group of the epoxy group-containing (meth)acrylic compound opens its ring, and it is a group having a hydroxyl group derived from the epoxy group and one (meth)acryloyl group.

[0025] The polymer P of this embodiment has an organic group containing a (meth)acryloyl group in its side chain, which is derived from a polyfunctional (meth)acrylic compound and an epoxy group-containing (meth)acrylic compound. Because the curing reaction (polymerization reaction) is promoted by the (meth)acryloyl group, polymer P has excellent sensitivity and high alkali solubility. Therefore, the photosensitive resin composition containing polymer P of this embodiment possesses both excellent alkali solubility and sensitivity, and as a result, when using a strongly basic developer such as tranmethylammonium hydroxide (TMAH) solution, the pattern after exposure and development can be made into the shape as designed.

[0026] The polymer P of this embodiment contains a thioether group in its structure derived from a monofunctional or bifunctional or more thiol group-containing compound used in the above-described step I. Because polymer P has a thioether group, it exhibits excellent sensitivity in photolithography and higher alkali solubility, thus providing a resin cured product with superior developability. Furthermore, because polymer P contains a thioether group, it reduces yellowing and provides a resin cured product with excellent transparency.

[0027] Furthermore, the polymer P of this embodiment has structural units derived from norbornene, represented by formula (NBm) used in the above-described step I. Structural units derived from norbornene monomer are chemically robust. Therefore, polymer P containing these structural units exhibits little weight loss and is stable when subjected to heat treatment.

[0028] Furthermore, the polymer P in this embodiment has styrene-derived structural units represented by formula (STm) used in the above-described step I. These styrene-derived structural units are also chemically robust. Therefore, polymer P containing these structural units exhibits minimal weight loss and is stable 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 that require heat resistance.

[0029] In one embodiment, step IIa for obtaining the first polymer precursor may be a step of reacting the raw material polymer with both the compound having a hydroxyl group and two or more (meth)acryloyl groups (a polyfunctional (meth)acrylic compound) and the 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. As a result, the first polymer precursor obtained and the polymer P obtained via the first polymer precursor have both side chains derived from the polyfunctional (meth)acrylic compound and side chains derived from the monofunctional (meth)acrylic compound.

[0030] In the design of typical photosensitive resin compositions, increasing curability to raise sensitivity tends to result in excessive curing and poor developability, while attempting to improve developability tends to result in insufficient curing. Therefore, it is preferable for polymer P to contain side chains derived from monofunctional (meth)acrylic compounds, thereby achieving a good balance between sensitivity and developability.

[0031] (Second Embodiment) In the second embodiment, polymer P is Step I involves polymerizing a monomer composition containing a monomer represented by the following formula (NBm), a monomer represented by the following formula (STm), and a monomer represented by the following formula (MAm) in the presence of a monofunctional or bifunctional or more thiol group-containing compound to prepare a raw material polymer. Step IIa: Reacting the raw material polymer with a compound having a hydroxyl group and two or more (meth)acryloyl groups in the presence of a basic catalyst to obtain a first polymer precursor. Step IIb: A step to obtain a second polymer precursor by treating the first polymer precursor with water in the presence of a catalyst, The polymer is obtained by a step (step III) in which the second polymer precursor is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst.

[0032] [ka]

[0033] In the formula (NBm), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2.

[0034] [ka]

[0035] In the formula (STm), R 10 , R 11 and R 12 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R 13 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms.

[0036] [ka]

[0037] In the formula (MAm), R 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0038] In the second embodiment, polymer P has, in addition to the structural units constituting polymer P in the first embodiment described above, structural units derived from maleic anhydride monomer represented by formula (MAm) contained in the first polymer precursor obtained in step IIa, which are ring-opened with water by the treatment in step IIb (dicarboxylic acid structural units). Such polymer P may have high alkali solubility, and as a result, the photosensitive resin composition containing polymer P has excellent developability when subjected to a photolithography method using an alkaline aqueous solution as a developer.

[0039] In one embodiment, step IIa for obtaining the first polymer precursor may be a step of reacting the raw material polymer with both the compound having a hydroxyl group and two or more (meth)acryloyl groups (a polyfunctional (meth)acrylic compound) and the 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. As a result, the first polymer precursor obtained and the polymer P obtained via the first polymer precursor have both side chains derived from the polyfunctional (meth)acrylic compound and side chains derived from the monofunctional (meth)acrylic compound.

[0040] (Third embodiment) In the third embodiment, polymer P has a structure represented by formula (P). Polymer P has a structure in which a polymer chain, typically composed of structural units A, B, and C, is bonded to a C1-C30 1-C6 valent organic group, represented as "Y" in formula (P), which is derived from a monofunctional or bifunctional or more thiol group-containing compound. This C1-C30 1-C6 valent organic group, derived from a monofunctional or bifunctional or more thiol group-containing compound, is typically a C1-C30 organic group containing 1-6 thioether groups.

[0041] [ka]

[0042] In equation (P), n is an integer between 1 and 6, preferably between 3 and 6. p, q, and r represent the molar content of structural units A, B, and C contained in each of the n polymer chains within the brackets, respectively. p, q, and r may be the same or different for each of the n polymer chains within the [ ]. p + q + r = 1, where p is greater than or equal to 0, q is greater than or equal to 0, and r is greater than or equal to 0. The molar content of each structural unit A, B, and C contained in the polymer is given by p t , q t , and r t Therefore, p t +q t +r t = 1, p t It is greater than 0, preferably 0.1 to 0.6, more preferably 0.2 to 0.5, and more preferably 0.25 to 0.45. q t It is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, and more preferably 0.35 to 0.60. r tIt is greater than 0, preferably 0.05 to 0.3, more preferably 0.06 to 0.28, and particularly preferably 0.07 to 0.25. p, q, or r may be the same or different for each of the n structural units within the [ ]. X is either hydrogen or an organic group with 1 to 30 carbon atoms. Y is a 1-30 carbon atom, 1-6 valent organic group derived from monofunctional or bifunctional or multi-functional thiol group-containing compounds. A represents a structural unit expressed by formula (NB). B includes structural units represented by formula (1-1) and structural units represented by formula (1-2). C represents a structural unit expressed by formula (ST). Multiple instances of A, B, or C may be identical or different.

[0043] [ka] In equation (NB), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2.

[0044] [ka] In equation (1-1), Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X represents an oxygen atom, a substituted or unsubstituted alkylene group with 1 to 4 carbon atoms, If Q is the alkyl group and X is the alkylene group, Q and X may condense to form a cyclic group. R 21 This refers to a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0045] [ka]

[0046] In formula (1-2), R p This is a group having two or more (meth)acryloyl groups, R 22 This refers to a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0047] [ka]

[0048] In formula (ST), R 10 , R 11 and R 12 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R 13 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms.

[0049] In the structural unit represented by the above formula (NB) that constitutes polymer P, R 1 ~R 4 Organic groups having 1 to 30 carbon atoms that can constitute these include saturated or unsaturated linear, branched, or cyclic hydrocarbon groups, alkoxy groups, heterocyclic groups, and carboxyl groups. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalyl groups, and cycloalkyl groups.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] In the structural unit represented by formula (NB), R 1 , R 2 , R 3 and R 4 Hydrogen or alkyl groups are preferred, with hydrogen being more preferred. Note, R 1 , R 2 , R 3 and R 4 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with fluorine atoms, hydroxyl groups, carboxyl groups, etc. More specifically, R 1 , R 2 , R 3 and R 4 As the organic group having 1 to 30 carbon atoms, alkyl groups such as fluoride may be selected. In the structural unit represented by formula (NB), a1 is preferably 0 or 1, more preferably 0.

[0054] The proportion of the structural unit represented by formula (NB) in the total structural units constituting polymer P is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, and even more preferably 25 to 45 mol%.

[0055] In the structural unit represented by the above formula (ST) that constitutes polymer P, R 10 , R 11 and R 12 Organic groups having 1 to 3 carbon atoms that can constitute this include methyl, ethyl, n-propyl, and isopropyl groups. 10 , R 11 and R 12 It is preferable that it be a hydrogen atom.

[0056] R in equation (ST) 13 Organic groups having 1 to 30 carbon atoms that can constitute these include substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic hydrocarbon groups, alkoxy groups, heterocyclic groups, and carboxyl groups. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalyl groups, and cycloalkyl groups.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] R in the structural unit represented by formula (ST) 13 R in the structural unit represented by formula (ST) 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. 10 , R 11 and R 12 , and R 13 By appropriately selecting R, the alkali solubility of the resulting polymer P can be adjusted. For example, R 13 By using a lower alkyl group, the alkali solubility of the resulting polymer P can be controlled. Note, R 13 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 13 As an organic group having 1 to 30 carbon atoms, alkyl groups such as fluoride may be selected.

[0061] The proportion of structural units represented by formula (ST) in the total structural units constituting polymer P is preferably 5 to 30 mol%, more preferably 6 to 28 mol%, and even more preferably 7 to 25 mol%. By setting the proportion of structural units represented by formula (ST) in polymer P within the above range, the balance of sensitivity, alkali solubility, and heat discoloration resistance of polymer P can be improved to a high level.

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

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

[0064] [Chemical formula]

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

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

[0067] In the structural unit represented by the above formula (1-2) constituting polymer P, R p represents a group containing two or more (meth)acryloyl groups. Preferably, R p is a group containing 2 to 9 (meth)acryloyl groups, and more preferably, is a group containing 3 to 6 (meth)acryloyl groups. By optimizing the number of (meth)acryloyl groups, the sensitivity of the resulting polymer P in the photolithography method can be increased. Also, sensitivity and developability can be balanced at a higher level, and furthermore, heat resistance can be improved.

[0068] The proportion of the structural unit represented by formula (1-2) in all the structural units of polymer P is preferably 1 to 30 mol%, more preferably 2 to 20 mol%.

[0069] In the structural unit represented by formula (1), R p 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. R pBy optimizing the number of (meth)acryloyl groups contained therein, the sensitivity in the exposure treatment of the polymer P containing the same can be further enhanced. Further, it becomes easier to more highly balance the sensitivity and the alkali solubility of the polymer P. Furthermore, the heat resistance of the polymer P can be improved.

[0070] R in formula (1) p is preferably a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d), and contains at least one selected from these. By being such a group, there is a tendency to easily obtain the above various effects.

[0071]

Chemical formula

[0072] In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different, X 1 is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and a plurality of Xs 1 may be the same or different, X 1 ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z' (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2 is a (k + 1)-valent organic group having 1 to 12 carbon atoms. R is preferably a hydrogen atom in view of further improvement in sensitivity (ease of polymerization) and the like. k may be 2 or 3, but is preferably 3 from the viewpoints of easy availability of raw materials and further improvement in sensitivity.

[0073] X 1 When is an alkylene group having 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).

[0074] 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)-.

[0075] 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.

[0076] X 2 As an organic group with 1 to 12 carbon atoms and a (k+1) valency, any group obtained by removing (k+1) hydrogen atoms from any organic compound can be cited. Here, "any organic compound" refers to, for example, an organic compound with a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less. 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 2The 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).

[0077] [ka]

[0078] 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 having 1 to 6 carbon atoms.

[0079] R, k, X 1 and X 2 The specific embodiments and preferred embodiments are the same as those described in 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.

[0080] [ka]

[0081] In equation (1d), n is an integer between 2 and 5, preferably 2 or 3. The specific and preferred embodiments of R are the same as those described in equation (1b).

[0082] Polymer P may contain a structural unit represented by the following formula (8), which consists of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-2).

[0083] [ka]

[0084] In equation (8), Q, X, and Z are equivalent to those in equation (1-1), and R p This is equivalent to equation (1-2). The proportion of the structural unit represented by formula (8) in the total structural units of polymer P is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%.

[0085] A polymer P having the structure represented by formula (P) may include structural units represented by formula (1-3) as structural units B.

[0086] [ka]

[0087] In formula (1-3), R s This is a group having one (meth)acryloyl group, R 22 This refers to a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0088] R in equation (1-3) S This is a group represented, for example, by the following formula (2a).

[0089] [ka]

[0090] In equation (2a), X 10 X is a divalent organic group, and R is either a hydrogen atom or a methyl group. 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. X 10 A preferred divalent organic group is, for example, an alkylene group. Some of the -CH2- groups in this alkylene group may be ether groups (-O-). The alkylene group may be linear or branched, but linear is more preferred.

[0091] 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 units represented by formula (1-3) become more readily involved in the crosslinking reaction, thereby increasing sensitivity.

[0092] 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.

[0093] As described above, in equation (1-3), R SThis 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 further contains structural units represented by formula (1-3), thereby achieving a good balance between sensitivity and developability.

[0094] The proportion of structural units represented by formula (1-3) in the total structural units of polymer P is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

[0095] Polymer P may contain a structural unit represented by the following formula (9), which consists of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-3).

[0096] [ka]

[0097] In equation (9), Z, Q, and X are equivalent to those in equation (1-1), and R S This is equivalent to equation (1-3).

[0098] When polymer P contains structural units represented by formula (9), the proportion of structural units represented by formula (9) in the total structural units of polymer P is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%.

[0099] A polymer P having the structure represented by formula (P) may include structural units represented by formula (1-4) as structural units B.

[0100] [ka]

[0101] In formula (1-4), R 22 This refers to a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0102] When polymer P contains structural units of formula (1-4), polymer P has both structural units containing a (meth)acryloyl group (the "-Z" group in formula (1-1)) represented by formula (1-1), and structural units containing a carboxyl group represented by formula (1-4). This (meth)acryloyl group contains a polymerizable carbon-carbon double bond. In this way, polymer P can be designed to have relatively large values ​​for both polymerizable groups and carboxyl groups because they are present within the same polymer molecule. In contrast, it is difficult to increase the content of both polymerizable groups and carboxyl groups in other resins such as (meth)acrylic resins. By having such a structure, polymer P can achieve a high level of both sensitivity and developability.

[0103] A polymer P having the structure represented by formula (P) may also contain the structural unit represented by formula (3) as structural unit B. By including the structural unit represented by formula (3) in addition to the structural units represented by formulas (1-1) and (1-2), the alkali solubility of polymer P can be adjusted. As a result, a photosensitive resin composition containing polymer P exhibits an excellent balance of sensitivity and developability even when subjected to photolithography using a strongly basic developer.

[0104] [ka]

[0105] In formula (3), R 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0106] When polymer P contains structural units represented by formula (3), the proportion of structural units represented by (3) in the total structural units of polymer P is preferably 1 to 15 mol%, more preferably 2 to 10 mol%.

[0107] Polymer P may contain a structural unit represented by the following formula (5), which consists of a structural unit represented by formula (1-1) and a structural unit represented by formula (1-4). By including this structural unit, a better balance between sensitivity and developability can be achieved.

[0108] [ka]

[0109] In equation (5), Z, X, and Q are equivalent to those in equation (1-1). When polymer P contains structural units represented by formula (5), the proportion of structural units represented by formula (5) in the total structural units of polymer P is preferably 1 to 12 mol%, more preferably 1 to 9 mol%.

[0110] From the viewpoint of the effects of the present invention, polymer P may further contain a structural unit represented by the following formula (6), which consists of two structural units represented by formula (1-1). By including this structural unit, sensitivity can be further improved.

[0111] [ka]

[0112] In equation (6), Z, X, and Q are equivalent to those in equation (1-1). Multiple Zs, multiple Qs, and multiple Xs may be the same or different.

[0113] When polymer P contains structural units represented by formula (6), the proportion of structural units represented by formula (6) in the total structural units of polymer P is preferably 1 to 10 mol%, more preferably 1 to 8 mol%.

[0114] A polymer P having the structure represented by formula (P) may include the structural unit represented by formula (1) as structural unit B.

[0115] [ka]

[0116] In formula (1), R p is a group having two or more (meth)acryloyl groups, and R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. When the polymer P contains a structural unit represented by formula (1), the proportion of the structural unit represented by formula (1) in all the structural units of the polymer P is preferably 0.5 to 25 mol%, more preferably 1 to 18 mol%.

[0117] The polymer P having the structure represented by formula (P) may contain a structural unit represented by formula (2) as the structural unit B.

[0118] [Chemical formula]

[0119] In formula (2), R s is a group having one (meth)acryloyl group, and R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. When the polymer P contains a structural unit represented by formula (2), the proportion of the structural unit represented by formula (2) in all the structural units of the polymer P is preferably 0.5 to 35 mol%, more preferably 2 to 25 mol%.

[0120] The polymer P having the structure represented by formula (P) may contain a structural unit represented by formula (MA) as the structural unit B.

[0121] [Chemical formula]

[0122] In formula (MA), R 21 and R 22Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0123] The structural unit represented by formula (MA) undergoes ring-opening with an alkaline developer to produce two carboxyl groups. Therefore, polymer P containing this structural unit exhibits excellent developability. When polymer P contains the structural unit represented by formula (MA), the amount of the structural unit represented by formula (MA) in the total structural units of polymer P is preferably 1 to 35 mol%, more preferably 2 to 30 mol%.

[0124] In 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 (NB) above. 1 ~R 4 It is similar to the organic group having 1 to 30 carbon atoms that makes up the compound.

[0125] In formula (P), Y is a C1-C30 1-6 valent organic group (i) derived from a monofunctional or bifunctional or more thiol group-containing compound (hereinafter referred to as "organic group (i)"). In this embodiment, the valency is the number of functional groups (number of thiol groups). That is, a monofunctional or bifunctional or more thiol group-containing compound contains one or more thiol groups, and organic group (i) is bonded to the structural units in [ ]n and [ ]m via 1-6 thioether groups derived from the thiol group. Organic group (i) may have thiol groups that are not involved in bonding to the structural units in [ ]n, and polymer P can be obtained as a mixture of each resin having n number (number of bonds) of 1-6. The organic group (i) having 1 to 30 carbon atoms is preferably bifunctional or more, more preferably trifunctional or more. The upper limit is not particularly limited, but it is 6-functional or less. From the viewpoint of the effects of the present invention, the valency of the organic group (i) having 1 to 30 carbon atoms is, for example, 1 to 6 valencies, preferably 2 to 6 valencies, and more preferably 4 to 6 valencies.

[0126] The 1-30 carbon-16 valent organic group (i) may contain one or more atoms selected from O, N, S, P, and Si. Examples of the 1-30 carbon-16 valent organic group (i) include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalil groups, cycloalkyl groups, alkoxy groups, and heterocyclic groups having 1-6 thioether groups (-S-* (* is a bond)).

[0127] 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.

[0128] 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.

[0129] 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.

[0130] Examples of the monofunctional or polyfunctional thiol group-containing compounds that can induce Y in formula (P) include compounds represented by the following chemical formulas (s-1) to (s-21). That is, polymer P contains a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound represented by the following.

[0131]

Chem.

[0132]

Chem.

[0133]

Chem.

[0134]

Chem.

[0135]

Chem.

[0136]

Chem.

[0137]

Chem.

[0138]

Chem.

[0139]

Chem.

[0140]

change

[0141]

change

[0142]

change

[0143]

change

[0144]

change

[0145]

change

[0146]

change

[0147]

change

[0148]

change

[0149]

change

[0150]

change

[0151] [ka]

[0152] Monofunctional or bifunctional thiol group-containing compounds may be used individually or in combination of two or more. In particular, thiol group-containing compounds with 3 to 6 thiol groups in a single molecule, which are 3 to 6 functional (3 to 6 valent), are preferred because they exhibit superior reactivity with other monomers. In this embodiment, the thiol group-containing compound more preferably includes compounds represented by chemical formulas (s-1) to (s-3), (s-5), and (s-8) to (s-10) among the compounds represented by chemical formulas (s-1) to (s-21), and more preferably includes compounds represented by chemical formulas (s-1) to (s-3), (s-5), and (s-9). The 1-6 valent organic group (i) having 1-30 carbon atoms has a thioether group (-S-* (* is a bond)) derived from the thiol group of these thiol-containing compounds at its terminus, and bonds to the structural units in [ ]n and [ ]m via the thioether group. The organic group (i) may also have a thiol group that does not participate in bonding to the structural units in [ ]n and [ ]m.

[0153] In this embodiment, when a tetrafunctional (tetravalent) thiol group-containing compound represented by the above formula (s-2) is used as the thiol group-containing compound with two or more functions, the polymer P can have a structure represented by the following formula (I).

[0154] [ka]

[0155] In formula (I), A, B, C, X, p, q, and r are equivalent to those in formula (P). However, for illustrative purposes in formula (I), p, q, and r for each polymer chain within the four brackets are represented as p 1 ~p 4 , q 1 ~q 4 , r 1 ~r 4 It should be written as follows. In equation (I), p 1 ~p 4 , q 1 ~q 4 , r 1 ~r 4 The polymer chains within the four brackets may be the same or different, p 1 +q 1 +r 1 =1, p 2 +q 2 +r 2 =1, p 3 +q 3 +r 3 =1, p 4 +q 4 +r 4 = 1 The molar content of each structural unit A, B, and C in the polymer represented by formula (I) is given by p t , q t , and r t Therefore, p t =p 1 +p 2 +p 3 +p 4 , q t =q 1 +q 2 +q 3 +q 4 , r t =r 1 +r 2 +r 3 +r 4 That is the case.

[0156] In formula (I), the bonding order of A, B, and C is not particularly limited, and any of A, B, or C may be bonded to the thioether group. Furthermore, although formula (I) is shown as an example in which the four structural units in [ ] are bonded via thioether groups derived from the four mercapto groups of the compound represented by chemical formula (s-2), it is also possible that 1 to 3 structural units in [ ] are bonded to the thioether groups derived from the four mercapto groups, and the remaining thioether groups are bonded to organic groups different from the structural units in [ ]. In this embodiment, polymer P can be obtained as a mixture containing at least one compound in which 1 to 4 of the structures in [ ] are bonded.

[0157] The content (ratio) of each structural unit contained in polymer P depends on the amount (moles) of raw materials used in the synthesis of polymer P, the amount of raw materials remaining after synthesis, and various spectra (e.g., IR spectrum). 1 H-NMR spectrum, 13 It can be estimated / calculated from the presence of peaks in the 1C-NMR spectrum and their peak areas.

[0158] The weight-average molecular weight Mw of polymer P in this embodiment is 2,000 to 80,000. Preferably, the weight-average molecular weight of polymer P is 4,000 to 70,000, more preferably 6,000 to 60,000, and even more preferably 7,000 to 50,000. By appropriately adjusting the weight-average molecular weight, the sensitivity and solubility in alkaline developers can be adjusted.

[0159] 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 1.25 to 4.5, and even more preferably 1.5 to 4.0. By appropriately adjusting the degree of dispersion, the physical properties of polymer P can be made homogeneous. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0160] 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 due to the inclusion of structural units represented by formula (NB) and formula (ST) in combination. This is advantageous in the manufacturing of liquid crystal displays and solid-state image sensors, as it allows for the stable existence of patterns formed on the substrate. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0161] The content (ratio) of each structural unit contained in the thioether group-containing (meth)acrylic resin (a) of 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.

[0162] The acid value of polymer P is 50 mg KOH / g or more and 150 mg KOH / g or less, preferably 55 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 650 g / mol or less, more preferably 250 g / mol or more and 600 g / mol or less. By having an acid value of 50 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.

[0163] 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.

[0164] 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.

[0165] 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).

[0166] 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).

[0167] 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, 1It can be estimated / calculated from the peak area of ​​the 1H-NMR spectrum, etc.

[0168] [Method for producing polymer P] The method for producing polymer P in this embodiment will be explained using the case where polymer P has a structure represented by formula (P) as an example.

[0169] The polymer P of this embodiment can be manufactured by the following steps I to III. Step I: A step of preparing a raw material polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (ST), a structural unit represented by formula (MA), and a 1-6 valent organic group (i) having 1 to 30 carbon atoms, and Step IIa: A step to prepare a first polymer precursor (a) which includes a structural unit represented by formula (NB), a structural unit represented by formula (ST), a 1-6 valent organic group having 1-30 carbon atoms (i), and a structural unit represented by formula (1-2), and optionally further including a structural unit represented by 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 (a polyfunctional (meth)acrylic compound) in the presence of a basic catalyst. Step III: A step to prepare polymer P, which contains a structural unit represented by formula (NB), a structural unit represented by formula (ST), an organic group (i) having 1 to 30 carbon atoms and 1 to 6 valent, a structural unit represented by formula (1-1), and a structural unit represented by formula (1-2), and optionally further containing a structural unit represented by formula (MA).

[0170] If polymer P further contains structural units represented by formula (1-3), the following step IIb is carried out following step IIa. Step IIb: A step in which a reaction mixture containing the polymer precursor obtained in Step IIa is reacted with a compound having a hydroxyl group and one (meth)acryloyl group (monofunctional (meth)acrylic compound) to obtain a first polymer precursor (b) containing a structural unit represented by formula (NB), a structural unit represented by formula (ST), a 1-6 valent organic group having 1 to 30 carbon atoms (i), a structural unit represented by formula (1-2), and a structural unit represented by formula (1-3), and optionally further containing a structural unit represented by formula (MA).

[0171] If polymer P further contains structural units represented by formula (3), the following step IIc is performed. Step IIc: A step in which the polymer precursor (a) or (b) obtained in Step IIa or Step IIb is treated with water in the presence of a base catalyst to obtain a first polymer precursor (c) which includes a structural unit represented by formula (NB), a structural unit represented by formula (ST), a 1-6 valent organic group having 1 to 30 carbon atoms (i), a structural unit represented by formula (1-2), a structural unit represented by formula (1-3), and a structural unit represented by formula (3), and optionally further including a structural unit represented by formula (MA). The following describes each step. (Process I) The step of preparing a raw material polymer in step (I) that includes a structural unit represented by formula (NB), a structural unit represented by formula (ST), a structural unit represented by formula (MA), and a C1-C30 C1-C6 valent organic group (i) can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (NBm), a monomer represented by formula (STm), and a monomer represented by formula (MAm) in the presence of a monofunctional or bifunctional or more thiol group-containing compound. Here, in formula (NBm), R 1 , R 2 , R 3 and R 4 Furthermore, the definition of a1 is the same as that in equation (NB). Also, R in equation (STm) 10 , R 11 , R 12 and R 13The definition of is the same as in equation (ST). Also, R in equation (MAm) 21 and R 22 The definition is the same as that in equation (MA).

[0172] [ka]

[0173] Examples of monomers represented by formula (NBm) include norbornene, bicyclo[2.2.1]-hepto-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, and 5-norbornene-2,3-dicarboxylic acid anhydride. During polymerization, the monomer represented by formula (NBm) may be used alone or in combination of two or more types.

[0174] [ka]

[0175] [ka]

[0176] Examples of monofunctional or bifunctional thiol group-containing compounds include, but are not limited to, the compounds represented by the above formulas (s-1) to (s-20). Monofunctional or bifunctional thiol group-containing compounds may be used individually or in combination of two or more.

[0177] While the polymerization method is not limited, radical polymerization using a radical polymerization initiator is preferred. Examples of polymerization initiators include azo compounds and organic peroxides. Specific examples of azo compounds include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonile) (ABCN). Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Regarding polymerization initiators, one type may be used alone, or two or more types may be used in combination.

[0178] For the polymerization reaction, organic solvents such as diethyl ether, tetrahydrofuran, toluene, and methyl ethyl ketone can be used as solvents. The polymerization solvent may be a single solvent or a mixture of solvents.

[0179] The synthesis of the raw material polymer is carried out by dissolving monomers represented by formula (NBm), monomers represented by formula (STm), monomers represented by formula (MAm), and a polymerization initiator in a solvent, charging them into a reaction vessel, and then heating them while adding monofunctional or bifunctional or more thiol group-containing compounds dropwise to allow addition polymerization to proceed. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours. When charging the reaction vessel, the molar ratio of the total amount of monomer represented by formula (NBm) and monomer represented by formula (STm) (NBm + STm) to the monomer represented by formula (MAm) is preferably (NBm + STm):(MAm) = 0.5:1 to 1:0.5. From the viewpoint of molecular structure control, a molar ratio of 1:1 is preferable. The molar ratio of monomer represented by formula (NBm) and monomer represented by formula (STm) is preferably (NBm):(STm) = 9.5:0.5 to 2:8, and more preferably 9:1 to 6:4. Furthermore, from the viewpoint of controlling the thioether group content in the resulting raw material polymer and the molecular weight of the raw material polymer, the amount of monofunctional or bifunctional or more thiol group-containing compound charged into the reaction vessel is preferably 0.5 to 10 mol%, more preferably 1 to 8 mol%, and even more preferably 1.5 to 6 mol%, relative to the total molar amount of monomer represented by formula (NBm), monomer represented by formula (STm), and monomer represented by formula (MAm). Through this process, "raw material polymers" can be obtained. The raw material polymer may be any of the following: random copolymer, alternating copolymer, block copolymer, or periodic copolymer. Typically, it is a random copolymer or alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability.

[0180] Furthermore, after the synthesis of the raw material polymer, a step may be taken to remove low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators. Specifically, the organic phase containing the synthesized raw material polymer and low molecular weight components is concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol to precipitate the monomers. By filtering and drying this precipitate, the purity of the raw material polymer can be increased.

[0181] (Step IIa) In step IIa, the raw material polymer obtained in step I is reacted with a polyfunctional (meth)acrylic compound in the presence of a basic catalyst. This causes some of the structural units represented by formula (MA) in the raw material polymer to open up, forming a structural unit represented by formula (1) that includes structural units represented by formulas (1-2) and (1-4). As a result, a polymer precursor (a) is obtained in which a structural unit containing a structural unit represented by formula (NB), a structural unit represented by formula (ST), and a structural unit represented by formula (1), and possibly a structural unit represented by formula (MA), is bonded to a 1-6 valent organic group (i) having 1-30 carbon atoms via 1-6 thioether groups.

[0182] More specifically, first, a solution is prepared by dissolving the raw material polymer in a suitable organic solvent. As the organic solvent, single or mixed solvents such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and tetrahydrofuran (THF) can be used, but are not limited to these; various organic solvents used in the synthesis of organic compounds and polymers can be used.

[0183] Examples of polyfunctional (meth)acrylic compounds that can be used here include the compound represented by formula (1b-m), the compound represented by formula (1c-m), and the compound represented by formula (1d-m). k, R, and X in formula (1b-m) 1 , X 1 'and X 2 The definition and specific form of are the same as in equation (1b) above. Also, k, R, and X in equation (1c-m) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific form of are the same as those in equation (1c) above. n and R in equation (1d-m) are the same as those in equation (1d) above.

[0184] [ka]

[0185] [ka]

[0186] [ka]

[0187] (Step IIb) Process IIb is a process that is performed as needed. In step IIb, the polymer precursor (a) obtained in step IIa is reacted with a monofunctional (meth)acrylic compound in the presence of a basic catalyst. This causes some of the structural units represented by formula (MA) in the polymer precursor (a) to undergo ring-opening, forming a structural unit represented by formula (2) that includes structural units represented by formulas (1-3) and (1-4). As a result, a polymer precursor (b) can be obtained in which structural units including structural units of formula (NB), formula (ST), formula (1), and formula (2), and optionally the structural unit represented by formula (MA), are bonded to the organic group (i) having 1 to 30 carbon atoms via 1 to 6 thioether groups.

[0188] As the basic catalyst used in step IIb, 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.

[0189] By heating the above solution at a temperature of preferably 60-80°C for about 3-9 hours, ring-opening of the structural unit of formula (MA) and formation of the structural unit of formula (2) are achieved in the raw material polymer.

[0190] Due to steric hindrance and other factors, monofunctional (meth)acrylic compounds containing hydroxyl groups tend to react more readily with the starting polymer than polyfunctional (meth)acrylic compounds containing hydroxyl groups. Therefore, when preparing a polymer precursor having the structural unit of formula (2), it is preferable to add a monofunctional (meth)acrylic compound containing hydroxyl groups to the reaction system in step IIa after or during step IIa. Examples of monofunctional (meth)acrylic compounds having a hydroxyl group include compounds represented by the following formulas (2a-m). In equation (2a-m), X 10 The definition of R is the same as that in equation (2a).

[0191] [ka]

[0192] Specific examples of compounds represented by formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalic acid.

[0193] (Process IIc) Process IIc is a process that is performed as needed. In step IIc, the polymer precursor (a) obtained in step IIa or the polymer precursor (b) obtained in step IIb is treated with water in the presence of a basic catalyst. Step IIc causes the structural unit represented by formula (MA) in the polymer precursor (a) or (b) obtained in step IIa or IIb to undergo ring-opening, forming the structural unit represented by formula (3), thereby producing a polymer precursor (c) containing a structure in which the structural unit represented by formula (NB), the structural unit represented by formula (ST), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (3) are bonded via a C1-C30 1-C6 valent organic group (i) and 1-6 thioether groups. If some of the structural unit represented by formula (MA) undergoes ring-opening and some of the structural unit of formula (MA) remains unringed, the polymer precursor (c) further contains the structural unit represented by formula (MA).

[0194] Basic catalysts used in step (IIc) include amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds.

[0195] In step IIc, water is added to the reaction system containing the polymer precursor (a) or (b) obtained in step IIa or step IIb, and the resulting reaction solution is heated, preferably at 60-80°C for about 0.25-6 hours, causing the structural unit of formula (MA) contained in the polymer precursor (a) or (b) to open its ring and generate the structural unit represented by formula (3). The basic catalyst can be the catalyst remaining in the reaction system obtained in step IIa (or step IIb, if applicable) which can be used as is. Therefore, it is preferable to carry out step IIIc by adding water to the reaction mixture obtained in step IIa or step IIb in situ without any post-treatment of the reaction mixture.

[0196] (Process III) In step III, the polymer precursor (a) obtained in step IIa, the polymer precursor (b) obtained in step IIb, or the polymer precursor (c) obtained in step IIc is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst. The reaction between the carboxyl groups of the polymer precursors (a) to (c) and the epoxy groups of the epoxy group-containing (meth)acrylic compound forms a structural unit represented by formula (1-1). This produces polymer P of this embodiment, which has a structure in which structural units including the structural unit represented by formula (NB), the structural unit represented by formula (ST), the structural unit represented by formula (1-1), and the structural unit represented by formula (1-2), and optionally the structural unit represented by formula (MA), are bonded to an organic group (i) having 1 to 30 carbon atoms via 1 to 6 thioether groups.

[0197] Step III is preferably carried out by adding an epoxy group-containing (meth)acrylic compound to a reaction system containing the polymer precursor (a) obtained in Step IIa, the polymer precursor (b) obtained in Step IIb, or the polymer precursor (c) obtained in Step IIc.

[0198] 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 same catalyst remaining in the reaction system obtained in step II. Therefore, it is preferable to carry out step III 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.

[0199] Specifically, the reaction solution obtained by adding an epoxy group-containing (meth)acrylic compound to a reaction mixture containing a polymer precursor is heated, preferably at 60-80°C, for about 1-9 hours. This reaction between the carboxyl groups of the polymer precursor and the epoxy groups of the epoxy group-containing (meth)acrylic compound forms a structural unit represented by formula (1-1), generating polymer P.

[0200] 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.

[0201] 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.

[0202] If polymer P is a polymer obtained via polymer precursor (a), polymer P contains a structure in which polymer chains comprising structural units represented by formula (NB), formula (ST), formula (8), formula (1), and formula (MA) are linked via organic groups (i) having 1 to 30 carbon atoms and 1 to 6 thioether groups.

[0203] If polymer P is a polymer obtained via polymer precursor (b), polymer P contains a structure in which polymer chains comprising structural units represented by formula (NB), formula (ST), formula (8), formula (9), formula (1), formula (2), and formula (MA) are linked via organic groups (i) having 1 to 30 carbon atoms and 1 to 6 thioether groups.

[0204] If polymer P is a polymer obtained via polymer precursor (c), polymer P contains a structure in which polymer chains comprising structural units represented by formula (NB), formula (ST), formula (8), formula (9), formula (5), formula (6), formula (1), formula (2), formula (3), and formula (MA) are linked via organic groups (i) having 1 to 30 carbon atoms and 1 to 6 thioether groups.

[0205] After step III, it is preferable to perform the following steps as appropriate to remove unwanted components other than the desired polymer P.

[0206] 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.

[0207] 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 P 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.

[0208] [Polymer solution] The polymer solution of this embodiment contains the polymer P described above. The polymer solution of this embodiment may contain, along with the polymer P, at least one selected from a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound.

[0209] (Polyfunctional (meth)acrylic compounds) The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that may be contained in the polymer solution of this embodiment may be unreacted (meth)acrylic compounds used in step IIa or step IIb in the production of polymer P, or may be added separately.

[0210] Examples of polyfunctional (meth)acrylic compounds that can be incorporated into polymer solutions include, but are not limited to, the compounds represented by the following formulas (1b-p), (1c-p), and (1d-p).

[0211] [ka]

[0212] [ka]

[0213] [ka]

[0214] k, R, X in equation (1b-p) 1 , X 1 'and X 2The definition and specific form of are the same as in equation (1b) above. Also, k, R, and X in equation (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 formula (1c) above.

[0215] In formulas (1b-p), (1c-p), and (1d-p), Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0216] Compounds in formulas (1b-p), (1c-p), and (1d-p) where Y is a hydrogen atom may be unreacted monomers (i.e., compounds represented by formulas (1b-p), (1c-p), and (1d-p)) and may be added separately. In equation (1d-p), n is an integer greater than or equal to 2, preferably an integer between 2 and 5, and more preferably an integer between 2 and 3.

[0217] 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 30% or less, more preferably 27.5% or less, and even more preferably 25% or less, relative to the peak area of ​​polymer P.

[0218] (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).

[0219] [ka]

[0220] 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.

[0221] 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.

[0222] 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.

[0223] [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.

[0224] [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.

[0225] (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.

[0226] 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.

[0227] (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.

[0228] 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.

[0229] 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.).

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] (Surfactants) The photosensitive resin composition of this embodiment may contain a surfactant, and a nonionic surfactant is preferred as the surfactant.

[0235] 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 with uniform thickness. Furthermore, it prevents residue and pattern lifting during the development of the coating film.

[0236] 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.

[0237] (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.

[0238] 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.

[0239] (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.

[0240] 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.

[0241] (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.

[0242] 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.

[0243] 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; Examples include polyfunctional aromatic vinyls such as divinylbenzene; and so on.

[0244] 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.

[0245] 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.

[0246] (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.

[0247] [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, spacers (e.g., photospacers, colored spacers, black spacers), and partition materials (e.g., transparent banks, black banks). 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 be obtained by forming a pattern using a photosensitive resin composition containing a light-shielding agent. Spacers or partition materials can also be obtained by forming a photosensitive resin composition. Thus, liquid crystal display devices and solid-state image sensors equipped with color filters, black matrices, spacers, or partition materials can be manufactured. This section describes a typical procedure for forming a pattern.

[0248] (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.

[0249] 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.

[0250] 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.

[0251] 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.

[0252] 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.

[0253] (exposure) Exposure is typically performed by irradiating a photosensitive resin film with active light through a suitable photomask.

[0254] 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.

[0255] 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.

[0256] (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.

[0257] 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.

[0258] 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.

[0259] 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.

[0260] 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.

[0261] 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.

[0262] The resulting pattern may also be heated to ensure sufficient curing. The heating temperature is typically 150-400°C, preferably 160-300°C, and more preferably 200-250°C. The heating time is not particularly limited, but is, for example, in the range of 15-300 minutes. This heat treatment can be carried out using a hot plate, an oven, or a heating oven with a temperature programmable. The atmospheric gas used during the heat treatment may be air, or an inert gas such as nitrogen or argon. Heating may also be carried out under reduced pressure. Figure 1 schematically shows an example of the structure of a liquid crystal display device and / or solid-state image sensor that includes a color filter and / or black matrix. While the black matrix may be replaced with a black bank, the following description focuses on liquid crystal display devices and / or solid-state image sensors that include both a color filter and a black matrix.

[0263] 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.

[0264] 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.

[0265] 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.

[0266] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted.

[0267] Further embodiments of the present invention are described below. [1] A process of preparing a raw material polymer by polymerizing a monomer composition containing a monomer represented by the following formula (NBm), a monomer represented by the following formula (STm), and a monomer represented by the following formula (MAm) in the presence of a monofunctional or bifunctional or more thiol group-containing compound, The process involves reacting the aforementioned raw material polymer with a compound having a hydroxyl group and two or more (meth)acryloyl groups in the presence of a basic catalyst to obtain a first polymer precursor. A method for producing a polymer, comprising the step of reacting the first polymer precursor with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst, [ka] In the formula (NBm), R 1 , R 2 , R 3 and R 4Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2. [ka] In the formula (STm), R 10 , R 11 and R 12 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R 13 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [ka] In the formula (MAm), R 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. A method for producing polymers. [2] A method for producing the polymer described in item [1], A method for producing a polymer, wherein the step of obtaining a first polymer precursor includes reacting the raw material polymer with a compound having a hydroxyl group and two or more (meth)acryloyl groups, and a compound having a hydroxyl group and one (meth)acryloyl group, in the presence of a basic catalyst. [3] A step of preparing a raw material polymer by polymerizing a monomer composition containing a monomer represented by the following formula (NBm), a monomer represented by the following formula (STm), and a monomer represented by the following formula (MAm) in the presence of a monofunctional or bifunctional or more thiol group-containing compound, The process involves reacting the aforementioned raw material polymer with a compound having a hydroxyl group and two or more (meth)acryloyl groups in the presence of a basic catalyst to obtain a first polymer precursor. A step of obtaining a second polymer precursor by treating the first polymer precursor with water in the presence of a catalyst, A method for producing a polymer, comprising the step of reacting the second polymer precursor with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst, [ka] In the formula (NBm), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2. [ka] In the formula (STm), R 10 , R 11 and R 12 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R 13 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [ka] In the formula (MAm), R 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. A method for producing polymers. [4] A method for producing the polymer described in item [3], A method for producing a polymer, wherein the step of obtaining a first polymer precursor includes reacting the raw material polymer with a compound having a hydroxyl group and two or more (meth)acryloyl groups, and a compound having a hydroxyl group and one (meth)acryloyl group, in the presence of a basic catalyst. [5] A method for producing a polymer as described in any of items [1] to [4], A polymer in which the monofunctional or bifunctional or more thiol group-containing compound is at least one compound selected from formulas (s-1) to (s-21). [ka] [6] A polymer solution comprising a polymer obtained by a polymer manufacturing method described in any of items [1] to [5]. [7] A polymer solution as described in item [6], A polymer solution further comprising a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof. [8] A polymer solution as described in item [6] or [7], A polymer solution used for forming color filters, black matrices, spacers, or partition materials. [9] A polymer obtained by a polymer manufacturing method described in any of items [1] to [5], A photoradical polymerization initiator, Photosensitive resin composition.

[10] A cured product formed from the photosensitive resin composition described in item [7]. [Examples]

[0268] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0269] The compounds used in the examples may be indicated by the following abbreviations or trade names. • MA: Maleic anhydride NB:2-Norbornen St: Styrene Vt: Vinyltoluene (4-methylstyrene) • MEK: Methyl ethyl ketone PEMP: Pentaerythritol tetrakis(3-mercaptopropionate) 4-HBA: 4-hydroxybutyl acrylate HEMA:2-hydroxyethyl methacrylate GMA: Glycidyl methacrylate • 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.).

[0270] [ka]

[0271] <Synthesis of raw material polymers> (Synthesis of raw material polymer 1) In a reaction vessel of appropriate size equipped with a stirrer and condenser, 353.02 g (3.6 mol) of maleic anhydride, 338.94 g (3.6 mol) of 2-norbornene, and 41.45 g (0.180 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed and placed. These were dissolved in a mixed solvent consisting of 578.98 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution. To this solution, nitrogen was passed through for 30 minutes to remove oxygen, and then the mixture was heated at 63°C for 9.5 hours while stirring to polymerize maleic anhydride and 2-norbornene, thereby preparing a polymerization solution. The polymerization solution obtained above was diluted with 712.92 g of methyl ethyl ketone, and then added dropwise to 8519.9 g of methanol to precipitate a white solid. The obtained white solid was vacuum-dried at 120°C to obtain 550.4 g of a polymer (raw material polymer 1) comprising structural units derived from 2-norbornene and structural units derived from maleic anhydride. GPC analysis of the obtained polymer revealed a weight-average molecular weight (Mw) of 11,600 and a polydispersity ratio (weight-average molecular weight (Mw) / (number-average molecular weight (Mn)) of 1.79.

[0272] (Synthesis of raw material polymer 2) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 602.56 g (451.92 g, 4.8 mol) of a 75% toluene solution of 2-norbornene, maleic anhydride (MA, 470.69 g, 4.8 mol), and 2238.50 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 dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 44.21 g, 0.19 mol) and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP, 140.73 g, 0.29 mol) dissolved in 189.74 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 908.1 g of polymer (raw material polymer 2) 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 2700, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.57.

[0273] (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.

[0274] [ka]

[0275] Raw material polymer 2 synthesized using PEMP 13In 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.

[0276] 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 the raw material polymer 2 has a skeleton containing a thioether group as described below, and the thiol group has disappeared.

[0277] [ka]

[0278] 13 The conditions for 1C-NMR measurement are as follows: (Test conditions) The measurement sample was prepared by adding the measurement solvent to the weighed sample to adjust the concentration, and then pouring the specified amount into an NMR measurement sample tube. • Measurement equipment: JEOL JNM-ECA400 superconducting FT-NMR spectrometer ·Resonance frequency: 100.53MHz • Measurement nucleus: 13 C • Measurement method: NNE measurement (inverse gate decoupling method) • Pulse width: 3.83 μsec • Pulse repetition waiting time: 30s • Total number of times: 4096 ·Measurement temperature: room temperature • Measurement solvent: DMSO-d6 (deuterated dimethyl sulfoxide) • Sample concentration: 20% (w / v) The amount of sulfur in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the polymer. Furthermore, GPC analysis of the reaction solution before methanol addition showed the disappearance of the PEMP-derived peak, confirming that PEMP was incorporated into the starting polymer 2.

[0279] (Synthesis of raw material polymer 3) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 122.40 g (1.18 mol) of styrene, 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 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, 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 3) 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 14,600, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 5.11. The amount of sulfur in the obtained raw material polymer 3 was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in raw material polymer 3. Furthermore, GPC measurement of the reaction solution did not show a peak for PEMP alone, indicating that no unreacted PEMP remained, thus confirming that PEMP was incorporated into raw material polymer 3. Also, raw material polymer 3 13 1C-NMR measurements confirmed that PEMP was incorporated into the raw material polymer 3.

[0280] (Synthesis of raw material polymer 4) In a reaction vessel of appropriate size equipped with a stirrer and condenser, 112.77 g (1.150 mol) of maleic anhydride and 115.49 g (equivalent to 86.62 g of 2-norbornene, 0.920 mol) of a 75% toluene solution of 2-norbornene were weighed and placed in the vessel. These were then dissolved in 149.16 g of methyl ethyl ketone to prepare a solution. To this solution, nitrogen was passed through for 30 minutes to remove oxygen, and then the solution was heated until the internal temperature reached 80°C. At this point, a solution of 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.59 g, 0.046 mol) and 23.95 g (0.230 mol) of styrene dissolved in 146.36 g of MEK was added over 1 hour. The reaction was then continued at 80°C for 7 hours. The reaction mixture was then cooled to room temperature to polymerize maleic anhydride, 2-norbornene, and styrene, and a polymerization solution was prepared. The polymerization solution obtained above was added dropwise to 2457.3 g of methanol to precipitate a white solid. The obtained white solid was further washed with 614.3 g of methanol and then vacuum-dried at 120°C to obtain 190.0 g of a polymer (raw material polymer 4) comprising structural units derived from 2-norbornene, structural units derived from styrene, and structural units derived from maleic anhydride.

[0281] The obtained raw material polymer 4 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 15,000, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 3.77.

[0282] (Synthesis of raw material polymer 5) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 115.49 g of a 75% toluene solution of 2-norbornene (equivalent to 86.62 g of 2-norbornene, 0.920 mol), maleic anhydride (MAN, 112.77 g, 1.150 mol), and 104.05 g of methyl ethyl ketone (MEK) were added and stirred until dissolved. Next, dissolved oxygen in the system was removed by nitrogen bubbling, and the mixture was heated until the internal temperature reached 80°C. Then, a solution of 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.59 g, 0.046 mol), styrene 23.95 g (0.230 mol), and PEMP (22.48 g, 0.046 mol) dissolved in 102.1 g of MEK was added over 1 hour. The reaction was then continued at 80°C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 2457.3 g of methanol to precipitate a white solid. The obtained white solid was further washed with 614.3 g of methanol and then vacuum-dried at 120°C to obtain 220.0 g of a polymer (raw material polymer 5) comprising structural units derived from 2-norbornene, structural units derived from styrene, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 4,700, and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.30. Regarding raw material polymer 5, 13 The ratio of structures derived from each monomer actually introduced into the raw material polymer, as calculated by 13C-NMR, was norbornene:styrene:maleic anhydride = 40.9%:10.7%:48.4%, and the amount of PEMP actually introduced into the raw material polymer was 1.9 mol% of the total amount of each monomer.

[0283] (Confirmation of the structure of raw material polymer 5) The amounts (mole fraction, mol%) of structural units derived from PEMP, styrene (structural units of formula (ST)), maleic anhydride (structural units of formula (MA)), and norbornene (structural units of formula (NB)) in raw material polymer 5 are as follows: 13The values ​​were calculated by integral analysis of 1C-NMR. 13 The 1C-NMR chart is shown in Figure 2. 13 The chemical shifts in the 1C-NMR chart were assigned to each structural unit as follows, and the corresponding integral values ​​were measured. PEMP k(4C): 62.0~64.0 ppm • Styrene aromatic ring (6C): 126.0~134.0 ppm • Maleic anhydride ester (2C) + PEMP g(4C): 170.0~174.7 ppm • Maleic acid ester (2C) (a structure in which maleic anhydride has been opened): 174.7~178.0 ppm Alkyl chain: 20-60 ppm • DMSO: around 40 ppm Norbornene(7C) = alkyl chain - DMSO - PEMP(9C, h+i+j) - maleic anhydride(2C) - maleic acid(2C) - styrene(2C) Here, the structural ratio derived from maleic anhydride that was actually introduced into the raw material polymer was calculated by including not only the structural unit of formula (MA) but also the structure of maleic acid obtained by ring-opening maleic anhydride.

[0284] The amount of sulfur in the obtained raw material polymer 5 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 5. Furthermore, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0285] (Synthesis of raw material polymer 6) Except for using 11.24 g (0.023 mol) of PEMP, the preparation was carried out in the same manner as for raw material polymer 5, and 128.1 g of polymer (raw material polymer 6) was obtained, which contained structural units derived from norbornene, styrene, and maleic anhydride. The obtained raw material polymer 6 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 6,700, and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.13.

[0286] The amount of sulfur in the obtained raw material polymer 6 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 6. Furthermore, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the raw material polymer 6. Also, the raw material polymer 6 13 1C-NMR measurements confirmed that PEMP was incorporated into the raw material polymer 6.

[0287] (Synthesis of raw material polymer 7) Except for using 86.62 g of a 75% toluene solution of 2-norbornene (equivalent to 64.96 g of 2-norbornene, 0.690 mol) and 47.91 g of styrene (0.460 mol), 118.0 g of polymer (raw polymer 7) was obtained in the same manner as raw polymer 6, comprising structural units derived from 2-norbornene, structural units derived from styrene, and structural units derived from maleic anhydride. The obtained raw polymer 7 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 8,900, and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.74.

[0288] The amount of sulfur in the obtained raw material polymer 7 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 7. Furthermore, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the raw material polymer 7. Also, the raw material polymer 7 13 1C-NMR measurements confirmed that PEMP was incorporated into the raw material polymer 7.

[0289] (Synthesis of raw material polymer 8) Except for replacing styrene with 27.18 g (0.230 mol) of vinyltoluene (Vt), the synthesis method was the same as for raw material polymer 5 to obtain 225.2 g of polymer (raw material polymer 8) comprising structural units derived from 2-norbornene, 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 4,500, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.90.

[0290] The amount of sulfur in the obtained raw material polymer 8 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 8. Furthermore, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0291] For raw material polymers 3-8, the amount of each monomer in the reaction solution before and after the reaction was measured by gas chromatography (GC), and the consumption of each monomer was calculated to determine the ratio of each monomer introduced into the raw material polymer. Table 1 below shows the charge ratio of monomers used in the synthesis of the raw material polymer, the ratio of monomers introduced into the raw material polymer as calculated by GC measurement, and the weight-average molecular weight (Mw) and heterodispersity (Mw / Mn) of the raw material polymer. The measurement conditions for gas chromatography are as follows: ·GC device: GC-2030 (Shimadzu Corporation) • Carrier gas: N2 • Detector: Flame ionization (FID) detector, FID temperature: 300℃ • Column: SH-RXi-1HT, inner diameter 0.25, length 30m, film thickness 0.25μm (Shimadzu GLC Co., Ltd.) • Evaporation chamber temperature: 210℃ Column flow rate: 0.64 mL / min • Column heating conditions: Hold at 50°C for 5 minutes, heat at 20°C / min up to 300°C, hold at 300°C for 10 minutes.

[0292] [Table 1]

[0293] <Synthesis of Polymer P> Polymer P was prepared using the following method.

[0294] (Preparation Example 1) Polymer P1 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). Details are described below. First, 100.30g of MEK was added to 60g of raw material polymer 1 (calculated as 0.312 moles of MA based on the amount of raw material polymer 1 used) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 56.27g (0.390 moles) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours to prepare the reaction solution. The phase was removed. The polymer was then purified using the reprecipitation method described below. (Reprecipitation method) 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, polymer P1 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. GPC analysis of polymer P1 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the resulting polymer P1 did not contain any unreacted (meth)acrylic compounds or (meth)acrylic compounds without hydroxyl groups. 1 1H-NMR measurements confirmed that polymer P1 has a ring-opened structure with A-TMM-3LM-N and 4-HBA.

[0295] (Preparation Example 2) The MA units of raw material polymer 1 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P2. Details are described below. First, 100.80g of MEK was added to 60g of raw material polymer 1 (calculated as 0.312 moles of MA based on the amount of raw material polymer 1 used) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 13.50g (0.094 moles) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours. Finally, 13.31g (0.094 moles) 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 same reprecipitation method as in Preparation Example 1.

[0296] Based on the above, polymer P2 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.

[0297] GPC analysis of polymer P2 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 P2 does not contain any unreacted (meth)acrylic compounds, hydroxyl group-less (meth)acrylic compounds, or unreacted epoxy group-containing (meth)acrylic compounds.

[0298] Furthermore, GPC measurements of the reaction solution before and after the ring-opening reaction and before and after the GMA addition reaction showed a decrease in the peak derived from the trifunctional (meth)acrylic compound (A-TMM-3LM-N) before and after ring-opening, and a decrease in the peak derived from GMA before and after the GMA addition reaction, confirming that A-TMM-3LM-N and GMA were introduced into the polymer.

[0299] (Preparation Example 3) Polymer P3 was prepared by ring-opening the MA units of raw material polymer 1 with a monofunctional (meth)acrylic compound (HEMA), and then reacting it with an epoxy group-containing (meth)acrylic compound (GMA). The details are explained below. First, 111.43g of MEK was added to 60g of raw polymer 1 (calculated as 0.312 moles of MA based on the amount of raw polymer 1 used) to prepare a solution. Next, 25.38g (0.195 moles) of HEMA was added to this solution, followed by 6.00g (0.059 moles) of triethylamine, and the mixture was reacted at 70°C for 6 hours. Subsequently, 13.31g (0.094 moles) 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 same reprecipitation method as in Preparation Example 1. Based on the above, polymer P3 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 P3 confirmed the disappearance of peaks for the monofunctional (meth)acrylic compound and the epoxy group-containing (meth)acrylic compound used. This confirmed that the obtained polymer P3 does not contain any unreacted (meth)acrylic compounds, (meth)acrylic compounds without hydroxyl groups, or unreacted epoxy group-containing (meth)acrylic compounds.

[0300] (Preparation Example 4) The MA units of raw material polymer 2 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P4. Details are described below. First, 100.14g of MEK was added to 60g of raw material polymer 2 (calculated as 0.312 moles of MA based on the amount of raw material polymer 2 used) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 56.27g (0.390 moles) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours. Finally, 26.62g (0.187 moles) 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 same reprecipitation method as in Preparation Example 1.

[0301] Based on the above, polymer P4 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.

[0302] GPC analysis of polymer P4 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 P4 does not contain any unreacted (meth)acrylic compounds, (meth)acrylic compounds without hydroxyl groups, or unreacted epoxy group-containing (meth)acrylic compounds.

[0303] (Preparation Example 5) The MA units of raw material polymer 3 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P5. Details are described below. First, 102.63g of MEK was added to 60g of raw polymer 3 (calculated as 0.297 moles of MA based on the amount of raw polymer 3 used) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 27.01g (0.187 moles) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours. Finally, 13.31g (0.094 moles) 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 same reprecipitation method as in Preparation Example 1.

[0304] Based on the above, polymer P5 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 3 with A-TMM-3LM-N and 4-HBA, and reacting them with GMA.

[0305] GPC analysis of polymer P5 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 P5 does not contain any unreacted (meth)acrylic compounds, (meth)acrylic compounds without hydroxyl groups, or unreacted epoxy group-containing (meth)acrylic compounds.

[0306] (Preparation Example 6) Polymer P6 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 4 with A-TMM-3LM-N and 4-HBA, and reacting them with GMA, in the same manner as in Preparation Example 5, except that 60g of raw material polymer 4 (0.309 moles in MA equivalent to the amount of raw material polymer 4 used) was used instead of raw material polymer 3.

[0307] 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 does not contain any unreacted (meth)acrylic compounds, hydroxyl group-less (meth)acrylic compounds, or unreacted epoxy group-containing (meth)acrylic compounds.

[0308] (Preparation Example 7) Polymer P7 was prepared by ring-opening the MA units of raw material polymer 4 with a monofunctional (meth)acrylic compound. Details are described below. First, 18.44 g of MEK was added to 10.00 g of raw polymer 4 (calculated as 0.051 moles in MA equivalent from the amount of raw polymer 4 used) to prepare a solution. Next, 9.38 g (0.065 moles) of 4-HBA was added to this solution, followed by 3.00 g (0.030 moles) of triethylamine, and the mixture was reacted at 70°C for 6 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase. The polymer was then purified using the same reprecipitation method as in Preparation Example 1. Based on the above, 8.7 g of polymer P7 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 4 with 4-HBA. Furthermore, GPC analysis of polymer P7 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P7 did not contain any unreacted monofunctional (meth)acrylic compound.

[0309] (Preparation Example 8) Polymer P8 was prepared in the same manner as in Preparation Example 7, except that 10.00 g of raw material polymer 5 (0.051 moles in MA equivalent, calculated from the amount of raw material polymer 5 used) was used instead of raw material polymer 4, by ring-opening the MA units of raw material polymer 5 with a monofunctional (meth)acrylic compound. 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.

[0310] (Preparation Example 9) Polymer P9 was prepared by ring-opening the MA units of raw material polymer 7 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. Details are described below. First, a solution was prepared by adding 99.93g of MEK to 60.00g of raw material polymer 7 (calculated from the amount of raw material polymer 1 used, equivalent to 0.306 moles of MA). Next, 77.49g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 56.27g (0.390 moles) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours to prepare the reaction solution. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70°C for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase. Further liquid-liquid extraction and subsequent solvent replacement were performed according to the following procedure. • Liquid-liquid extraction: The reaction solution was diluted with MEK, then water was added and treated to remove the aqueous phase from the reaction solution, and the same procedure was repeated once more. • Solvent Replacement: The 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 solvent was removed under reduced pressure at 50°C using the same procedure, and the solid content concentration was adjusted to 27±2 mass% by measurement using a heat-drying type moisture meter. This process of adding PGMEA to bring the solid content concentration to 18 mass% and mixing until homogeneous was repeated two more times. Then, the solvent was removed or PGMEA was added and stirred until homogeneous was achieved 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. Subsequently, the polymer was further purified using the same reprecipitation method as in Preparation Example 1. Based on the above, polymer P9 was prepared by ring-opening the structural units derived from maleic anhydride in raw material polymer 7 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. Furthermore, GPC analysis of polymer P9 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P9 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P9 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0311] (Preparation Example 10) Polymer P10 was prepared by ring-opening the MA units of raw material polymer 5 with a monofunctional (meth)acrylic compound (HEMA), and then reacting it with an epoxy group-containing (meth)acrylic compound (GMA). The details are explained below. First, 252.42g of MEK was added to 60g of raw polymer 5 (calculated as 0.309 moles of MA based on the amount of raw polymer 5 used) to prepare a solution. Next, 56.27g (0.390 moles) of 4-HBA was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 6 hours. Subsequently, 13.31g (0.094 moles) 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 same reprecipitation method as in Preparation Example 1. Based on the above, polymer P10 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 5 with 4-HBA and reacting them with GMA. GPC analysis of polymer P10 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic compound and the epoxy group-containing (meth)acrylic compound used. This confirmed that the obtained polymer P10 does not contain any unreacted (meth)acrylic compounds, (meth)acrylic compounds without hydroxyl groups, or unreacted epoxy group-containing (meth)acrylic compounds.

[0312] (Preparation Example 11) Except for using 60g of raw material polymer 5 (0.309 moles in MA equivalent, calculated from the amount of raw material polymer 5 used) instead of raw material polymer 3, the procedure was the same as in Preparation Example 5. The structural units derived from maleic anhydride in raw material polymer 5 were ring-opened with A-TMM-3LM-N and 4-HBA, and polymer P11 was obtained by reacting with GMA.

[0313] GPC analysis of polymer P11 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 P11 does not contain any unreacted (meth)acrylic compounds, (meth)acrylic compounds without hydroxyl groups, or unreacted epoxy group-containing (meth)acrylic compounds.

[0314] Figure 3 shows polymer P11 1 The H-NMR chart of polymer P11 in Figure 3 is shown. 1 In addition to the peak corresponding to the 3H of the acryloyl group (-CH=CH2) at 5.8–6.7 ppm shown in the H-NMR chart, peaks corresponding to the 2H of the methacryloyl group (-C(CH3)=CH2) (-C(CH3)=CH2's CH2) appeared at 5.6–5.8 ppm and 6.0–6.1 ppm, indicated by ×. In the GPC measurement of polymer P11, the absence of peaks for unreacted trifunctional (meth)acrylic compounds (A-TMM-3LM-N), monofunctional (meth)acrylic compounds (4-HBA), and epoxy group-containing (meth)acrylic compounds (GMA) indicates that acryloyl groups and methacryloyl groups derived from GMA were introduced into the polymer.

[0315] Furthermore, GPC measurements of the reaction solution before and after the ring-opening reaction and before and after the GMA addition reaction showed a decrease in the peak derived from the trifunctional (meth)acrylic compound (A-TMM-3LM-N) before and after ring-opening, and a decrease in the peak derived from GMA before and after the GMA addition reaction, indicating that A-TMM-3LM-N and GMA were introduced into the polymer.

[0316] (Preparation Example 12) The MA units of raw material polymer 7 were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P12. In detail, polymer P12 was obtained by using 60g of raw material polymer 7 (equivalent to 0.306 moles of MA calculated from the amount of raw material polymer 5 used) instead of raw material polymer 5, and using 38.75g of A-TMM-3LM-N, 28.13g of 4-HBA (0.195 moles), and 19.97g of GMA (0.140 moles) in the same manner as in Preparation Example 11. The structural units derived from maleic anhydride in raw material polymer 7 were ring-opened with A-TMM-3LM-N, 4-HBA, and water, and reacted with GMA to obtain polymer P12. GPC analysis of polymer P12 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 P12 does not contain any unreacted (meth)acrylic compounds, (meth)acrylic compounds without hydroxyl groups, or unreacted epoxy group-containing (meth)acrylic compounds.

[0317] (Preparation Example 13) Polymer P13 was prepared by opening the MA units of raw material polymer 6 with a trifunctional (meth)acrylic compound (A-TMM-3LM-N), further opening the rings by adding water, and then reacting it with an epoxy group-containing (meth)acrylic compound (GMA). The details are explained below. First, 297.25g of MEK was added to 60g of raw polymer 6 (calculated as 0.309 moles of MA based on the amount of raw polymer 6 used) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 0.60g (0.033 moles) of water was added, and the mixture was reacted at 70°C for 2 hours. Finally, 26.62g (0.187 moles) 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 same reprecipitation method as in Preparation Example 1. Based on the above, polymer P13 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 6 with A-TMM-3LM-N and water, and reacting them with GMA. GPC analysis of polymer P13 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic compound and epoxy group-containing (meth)acrylic compound used. This confirmed that the obtained polymer P13 does not contain unreacted (meth)acrylic compounds, (meth)acrylic compounds without hydroxyl groups, or unreacted epoxy group-containing (meth)acrylic compounds.

[0318] (Preparation Example 14) 100 parts by mass of polymer P12 obtained in Preparation Example 12 and 10 parts by mass of A-TMM-3LM-N were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to obtain polymer solution P14 with a solid content (total amount of polymer P12 and A-TMM-3LM-N) concentration of 30% by mass.

[0319] (Preparation Example 15) 100 parts by mass of polymer P13 obtained in Preparation Example 13 and 20 parts by mass of A-TMM-3LM-N were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to obtain polymer solution P15 with a solid content (total amount of polymer P13 and A-TMM-3LM-N) concentration of 30% by mass.

[0320] (Preparation Example 16) Except for using 60g of raw material polymer 8 (0.304 moles in MA equivalent, calculated from the amount of raw material polymer 8 used) instead of raw material polymer 3, the procedure was the same as in Preparation Example 5. The structural units derived from maleic anhydride in raw material polymer 8 were ring-opened with A-TMM-3LM-N and 4-HBA, and polymer P16 was obtained by reacting with GMA.

[0321] GPC analysis of polymer P16 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 P16 does not contain any unreacted (meth)acrylic compounds, (meth)acrylic compounds without hydroxyl groups, or unreacted epoxy group-containing (meth)acrylic compounds.

[0322] (Preparation Example 17) Polymer P17 was prepared by ring-opening the MA units of raw material polymer 8 with a trifunctional (meth)acrylic compound (A-TMM-3LM-N), then reacting it with an epoxy group-containing (meth)acrylic compound (GMA), and finally ring-opening it with water. The details are explained below. First, 297.25g of MEK was added to 60g of raw polymer 8 (calculated as 0.304 moles of MA based on the amount of raw polymer 8 used) to prepare a solution. Next, 58.12g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. After that, 19.97g (0.140 moles) 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 the aqueous phase was removed from the reaction solution by treatment with aqueous formic acid and aqueous citric acid solutions. Subsequently, the polymer was purified using the same liquid-liquid extraction and solvent replacement method as in Preparation Example 9. Next, 30% by mass of water relative to the polymer solids was added to this polymer solution, and the reaction was carried out at 70°C for 18 hours to perform water hydrolysis. The solution after the reaction was then subjected to solvent replacement according to the following procedure. • Solvent Replacement: PGMEA was added to the resulting reaction mixture so that the solid content concentration was 18% by mass, and the mixture was mixed until homogeneous. Then, the solvent was removed 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% by mass as measured by a heat-drying moisture meter. The same procedure was repeated two more times, where PGMEA was added to bring the solid content concentration to 18% by mass, mixed until homogeneous, and then the solvent was removed under reduced pressure at 50°C to adjust the solid content concentration to 27±2% by mass as measured by a heat-drying moisture meter. Then, the solvent was removed or PGMEA was added and stirred until homogeneous as the solid content concentration reached 30±3% by mass. Through these operations, the water used in the reaction was removed and the solvent was replaced with PGMEA. Based on the above, a polymer solution P17 was obtained in which the structural units derived from maleic anhydride in the raw material polymer 8 were ring-opened with A-TMM-3LM-N, reacted with GMA, and then ring-opened with water, and the polymer solution P17 contained the polymer P17 and the remaining (free) A-TMM-3LM-N. The obtained polymer solution P17 was analyzed by gel permeation chromatography to determine the amount of polymer P17 and free polyfunctional (meth)acrylic compound contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P17. The results are shown in Table 2. The amount of free (meth)acrylic compound is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compound relative to the peak area of ​​polymer P17 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0323] (Physical property measurement) (molecular weight) GPC measurements were performed on the obtained polymers P1-P13, P16, and P17 to determine their weight-average molecular weight and polydispersity. The results are shown in Table 2.

[0324] (Acid value) The acid value of the polymer was measured by the following method. Approximately 50 mg of polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. This solution was then analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 1H-NMR measurements were performed. 1 The amount of carboxyl groups is determined by using the integral value of the 4H peak (around 8.1 ppm) of the phenyl group of the dimethyl terephthalate, an internal standard in 1H-NMR measurements, as a reference, and then using the integral value of the H peak (around 12.4 ppm) of the carboxyl group (-COOH) of the polymer. From this amount, the acid value (mgKOH / g) can be calculated. A higher acid value indicates a greater amount of carboxyl groups per unit mass of polymer. The results are shown in Table 2. An acid value of 50 gKOH / g or higher indicates that the polymer contains sufficient carboxyl groups necessary for adequate development.

[0325] (double bond equivalent) The double bond equivalents of the polymer were measured using the following method. Similar to the above method for measuring acid value, 1¹H-NMR measurements were performed. The amount of acryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal originating from acryloyl groups (5.6-5.8 ppm, 3H) and the signal of the phenyl group of the internal standard (8.1 ppm, 4H) in the obtained spectral chart. The amount of methacryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal originating from methacryloyl groups (5.6-5.8 ppm, 2H) and the signal of the phenyl group of the internal standard (8.1 ppm, 4H). Here, the signal originating from methacryloyl groups at 6.0-6.1 ppm was negligible and overlapped with the signal of acryloyl groups, so it was calculated as the signal of acryloyl groups. The amount of double bonds (mol / g) was calculated from the sum of the calculated amount of acryloyl groups (mol / g) and methacryloyl groups (mol / g) in the polymer, and the double bond equivalent (g / mol) was calculated from the double bond amount. The results are shown in Table 2. A smaller double bond equivalent value indicates a larger amount of C=C double bonds per unit mass of polymer. 1 Table 2 shows the introduction ratio (moles) of each structural unit to maleic anhydride, calculated by 1H-NMR.

[0326] [Table 2] [Table 3]

[0327] (Examples 1-7, Comparative Examples 1-10) In each example and comparative example, resin compositions and photosensitive resin compositions were prepared and evaluated for the following items. [Alkali dissolution rate of resin compositions] Polymers P1-P13 and P16 obtained in Preparation Examples 1-13 and 16 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1-13 and 16 with a solid content concentration of 30% by mass. Next, resin compositions 14, 15, and 17, consisting of the above resin compositions 1 to 13, 16, or polymer solutions P14, P15, and P17 obtained in preparation examples 14, 15, and 17, were spin-coated onto wafers, 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 2.38 mass% TMAH aqueous solution at 23°C, and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and then dividing the film thickness by that time. The results are shown in Table 3. If the alkali dissolution rate is between 100 nm / s and 1,400 nm / s, it can be used without problems; if it is between 300 nm / s and 1,000 nm / s, it can be considered to have good developability; if it is between 500 nm / s and 900 nm / s, it can be considered to have even better developability; and if it is between 600 nm / s and 800 nm / s, it can be considered to have particularly good developability.

[0328] [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-P13, P16 (polymers P from Preparation Examples 1-13 and 16, respectively) or resin compositions 14, 15, and 17 (polymer solutions P14, P15, and P17 from Preparation Examples 14, 15, and 17, respectively): 100 parts by mass (Here, resin compositions 14, 15, and 17 were weighed so that the total amount of solids (polymers P14, P15, and P17) and the polyfunctional (meth)acrylic compound was 100 parts by mass.) • Polyfunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-DPH): 50 parts by mass • Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by mass • Adhesion enhancer (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass • Surfactant (manufactured by DIC Corporation, F-556): 0.5 parts by mass

[0329] 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 2.38 mass% TMAH aqueous solution at 23°C for 10 seconds (wafer immersion) to achieve a radiation level of 1-100 mJ / cm². 2 Thin films B were obtained by exposing and developing them at each exposure level. The residual film percentage was calculated from the film thicknesses of thin films A and B obtained by the above method using the following formula. Residual film percentage (%) = (Film thickness of thin film B at each exposure dose / Film thickness of thin film A) × 100 The exposure dose at which a residual film rate of 90% or more was determined as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. The exposure dose at which a residual film rate of 90% or more was 15 mJ / cm² 2 If the following conditions are met, it can be used without problems as a photosensitive composition, up to 13 mJ / cm². 2 If the following is true, the sensitivity can be considered good: 10 mJ / cm² 2 The following can be considered better, and even better, 8 mJ / cm². 2 The following can be considered particularly good.

[0330] [Sensitivity evaluation of photosensitive resin composition 2 (exposure amount at which the residual film rate is 95% or more)] In the same manner as described above for measuring the exposure dose at which the residual film rate was 90% or higher, the exposure dose at which the residual film rate was 95% or higher was measured. The results are shown in Table 3. The exposure dose at which the residual film rate is 95% or higher is 15 mJ / cm². 2 If the following conditions are met, it can be used without problems as a photosensitive composition, up to 13 mJ / cm².2 If the following is true, the sensitivity can be considered good: 10 mJ / cm² 2 The following can be considered better, and even better, 8 mJ / cm². 2 The following can be considered particularly good.

[0331] [Sensitivity evaluation of photosensitive resin composition 3 (exposure amount at which the residual film rate is 99% or higher)] In the same manner as described above for measuring the exposure dose at which the residual film rate was 90% or higher, the exposure dose at which the residual film rate was 99% or higher was measured. The results are shown in Table 3. The exposure dose at which the residual film rate exceeds 95% is 20 mJ / cm². 2 If the following conditions are met, it can be used without problems as a photosensitive composition, up to 15 mJ / cm². 2 The sensitivity can be considered good if it is below 13 mJ / cm². 2 The following can be considered better, and an additional 10 mJ / cm² is also acceptable. 2 The following can be considered particularly good.

[0332] [Alkaline dissolution rate of photosensitive resin composition (2.38% by mass TMAH aqueous solution)] The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above was spin-coated onto a wafer, the PGMEA was dried, and then a resin film with a thickness of approximately 2 μm was fabricated by pre-baking at a temperature of 100°C for 2 minutes. The resin film, along with the wafer, was immersed in a 2.38 mass% TMAH 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 3. If the alkali dissolution rate is between 200 nm / s and 3,500 nm / s, it can be used without problems; if it is between 300 nm / s and 3,000 nm / s, it can be considered to have good developability; if it is between 500 nm / s and 2,500 nm / s, it can be considered to have even better developability; and if it is between 700 nm / s and 2,000 nm / s, it can be considered to have particularly good developability.

[0333] [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 2.38 mass% TMAH aqueous solution at 23°C for 10 seconds (wafer immersion) to achieve a radiation level of 100 mJ / cm². 2 A thin film was obtained by exposing and developing it with the specified exposure level. The thin film was heat-treated at 230°C for 30 minutes under air conditions. After the thin film was cooled under air conditions at room temperature, it was heat-treated again at 230°C for 30 minutes under air conditions. The same procedure was repeated, and the heat treatment under air for 30 minutes was performed a total of three times. The yellow index (YI) of the thin film obtained by the above method was measured three times at different measurement points using a CR-5 colorimeter (manufactured by Konica Minolta), and the average value was taken as the YI value. The measurement type was transmission measurement, and 100% calibration was performed using uncoated Eagle XG glass (manufactured by Corning, thickness 0.5 mm). The results are shown in Table 3. If the yellow index is 1.15 or less, it can be used without problems as a photosensitive material; if it is 1.10 or less, it can be considered to have good heat discoloration resistance; if it is 1.00 or less, it can be considered to have better resistance; and if it is 0.80 or less, it can be considered to have particularly good resistance.

[0334] [Adhesion during development] (Adhesion to line patterns) A photosensitive resin composition was rotary coated onto Eagle XG glass (manufactured by 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 is exposed to 18 mJ / cm² of light using a Canon g+h+i-ray mask aligner (PLA-501F) via a photomask having five alternating glass sections (exposure areas) measuring 40 μm wide and 400 μm long, and chromium sections (light-shielding areas) also measuring 40 μm wide and 400 μm long. 2 The g+h+i line was exposed with the specified exposure dose. This exposure exposed the glass portion of the photomask to the specified dose because it transmits light, while the chromium portion remained unexposed because it does not transmit light, resulting in a line pattern with alternating exposed and unexposed areas. After exposure, the thin film was developed in a 0.5% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (wafer immersion), resulting in a density of 18 mJ / cm². 2 Thin films were obtained by exposure and development at the specified exposure levels. After exposure and development, five line patterns measuring 40 μm in width and 400 μm in height were observed under a microscope to check for peeling of the line patterns. (Judgment criteria) ○: The line pattern after development was in close contact with the substrate, and no areas of peeling were observed. ×: In the line pattern after development, areas that had peeled off from the substrate were observed.

[0335] (Adhesion to the dot pattern) A photosensitive resin composition was rotary coated onto Eagle XG glass (manufactured by 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 is exposed to 18 mJ / cm² of light using a Canon g+h+i ray mask aligner (PLA-501F) via a photomask that has a total of three patterns, each consisting of a 50 μm wide x 50 μm long glass section (exposure area) surrounded by a chromium section (light-shielding area). 2The g+h+i line was exposed with the specified exposure dose. This exposure exposed the glass portion of the photomask to the specified dose because it transmits light, while the chromium portion remained unexposed because it does not transmit light, resulting in a dot pattern with an exposure area of ​​50 μm in width and 50 μm in height. After exposure, the thin film was developed in a 0.5 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (wafer immersion), resulting in a light absorption rate of 18 mJ / cm². 2 Thin films were obtained by exposure and development at the specified exposure levels. Three dot patterns, each 50 μm wide and 50 μm long, were observed under a microscope to check for the presence or absence of line pattern peeling after exposure and development. (Judgment criteria) ○: The dot pattern after development was firmly attached to the substrate, and no areas of peeling were observed. ×: In the developed dot pattern, areas that had peeled off from the substrate were observed.

[0336] The results are shown in Table 3. If the adhesion of the line pattern is judged as "○", it can be used without problems as a photosensitive material, and if the adhesion of the dot pattern is judged as "○", it can be considered to have particularly good adhesion.

[0337] [Table 4]

[0338] The photosensitive resin compositions of Examples 1 to 7 had suitable solubility for strong base development, good sensitivity, reduced yellowing, excellent transparency, and excellent adhesion to substrates and the like.

[0339] <Making color filters / spacers> To the photosensitive resin compositions prepared in Examples 1 to 7, an appropriate amount of pigment dispersion NX-061 (manufactured by Dainichi Seika Kogyo Co., Ltd., green) was added to prepare a colored photosensitive resin composition. By forming this film on a substrate and then performing processes such as exposure and alkaline development, we were able to create a green color filter and spacer. Furthermore, by using NX-053 (blue) or NX-032 (red), also manufactured by the same company, as pigment dispersions instead of NX-061, it was possible to form blue or red color filters and spacers.

[0340] <Creation of Black Matrix / Black Bank / Black Spacer> To the photosensitive resin compositions prepared in Examples 1 to 7, an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichi Seika Kogyo Co., Ltd.) was added to prepare a black photosensitive resin composition. By depositing this onto a substrate and performing processes such as exposure and alkaline development, we were able to form a black matrix / black bank / black spacer. [Explanation of Symbols]

[0341] 10 circuit boards 11 Black Matrix 12 Color Filters 13 Protective film 14 Transparent electrode layer

Claims

1. A polymer having a structure represented by formula (P), 【Chemistry 1】 In equation (P), n is an integer between 1 and 6. p, q, and r represent the molar content of A, B, and C contained in each of the n polymer chains within the brackets, respectively. p, q, and r may be the same or different for each of the n polymer chains within the brackets. p + q + r = 1, where p is greater than or equal to 0, q is greater than or equal to 0, and r is greater than or equal to 0. When the molar contents of each of the structural units A, B, and C contained in the polymer are p ｔ , q ｔ , and r ｔ respectively, then p ｔ + q ｔ + r ｔ = 1, p ｔ is greater than 0, q ｔ is greater than 0, r ｔ is greater than 0, X is hydrogen or an organic group having 1 to 30 carbon atoms. Y is a C1-C30 1-C6 valent organic group derived from monofunctional or bifunctional or multi-functional thiol group-containing compounds. A represents a structural unit represented by formula (NB), B includes structural units represented by formula (1-1) and structural units represented by formula (1-2), C represents a structural unit represented by formula (ST), Multiple A's, B's, and C's may be the same or different. 【Chemistry 2】 In equation (NB), R １ , R ２ , R ３ and R ４ Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a １ is 0, 1, or 2, 【Transformation 3】 In formula (1-1), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X represents an oxygen atom, a substituted or unsubstituted alkylene group with 1 to 4 carbon atoms, When Q is the alkyl group and X is the alkylene group, Q and X may condense to form a cyclic group. R ２１ This is a hydrogen atom or an organic group having 1 to 3 carbon atoms. 【Chemistry 4】 In formula (1-2), R ｐ This is a group having two or more (meth)acryloyl groups, R ２２ This is a hydrogen atom or an organic group having 1 to 3 carbon atoms. 【Transformation 5】 In formula (ST), R １０ , R １１ and R １２ Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, R １３ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 30 carbon atoms.

2. The polymer according to claim 1, The aforementioned B further includes a structural unit represented by formula (1-3), 【Transformation 6】 In formula (1-3), R ｓ This is a group having one (meth)acryloyl group, R ２２ A polymer is a polymer consisting of a hydrogen atom or an organic group with 1 to 3 carbon atoms.

3. The polymer according to claim 1, The aforementioned B further includes a structural unit represented by formula (1-4), 【Transformation 7】 In formula (1-4), R ２２ A polymer is a polymer consisting of a hydrogen atom or an organic group with 1 to 3 carbon atoms.

4. The polymer according to claim 1, The aforementioned B further includes a structural unit represented by formula (1), 【Transformation 8】 In formula (1), R ｐ R is a group having two or more (meth)acryloyl groups, ２１ and R ２２ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms.

5. The polymer according to claim 1, The aforementioned B further includes a structural unit represented by formula (2), 【Chemistry 9】 In formula (2), R ｓ This is a group having one (meth)acryloyl group, R ２１ and R ２２ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms.

6. The polymer according to claim 1, The aforementioned B further includes a structural unit represented by formula (3), 【Chemistry 10】 In formula (3), R ２１ and R ２２ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms.

7. The polymer according to claim 1, The aforementioned B further includes a structural unit represented by formula (MA), 【Chemistry 11】 In formula (MA), R ２１ and R ２２ Each of these is an independent polymer consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms.

8. The polymer according to claim 1, The aforementioned R ｐ is at least one selected from the group represented by formula (1b), the group represented by formula (1c), and the group represented by formula (1d), 【Chemistry 12】 In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different. X １ X is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented as -Z-X- (where Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X groups. １ They may be the same or different. X １ ' represents a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (where X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X ２ This is an organic group with 1 to 12 carbon atoms and a (k+1) valency. 【Chemistry 13】 In formula (1c), k, R, X １ and X ２ These are R, k, and X in equation (1b), respectively. １ and X ２ This is synonymous with multiple Rs, which may be the same or different from each other, and multiple X １ They may be the same or different from each other. X ３ This is a single bond or a divalent organic group having 1 to 6 carbon atoms. X ４ and X ５ Each of these is independently a single bond or a divalent organic group having 1 to 6 carbon atoms. X ６ It is a divalent organic group having 1 to 6 carbon atoms. 【Chemistry 14】 In formula (1d), n is an integer between 1 and 5. R is independently either a hydrogen atom or a methyl group. polymer.

9. The polymer according to claim 2, The aforementioned R ｓ This is a base represented by formula (2a), 【Chemistry 15】 In formula (2a), X １０ R is a divalent organic group, and R is either a hydrogen atom or a methyl group. polymer.

10. The polymer according to claim 1, In the above formula (ST), R １３ A polymer comprising a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or a carboxyl group.

11. The polymer according to claim 1, wherein the weight-average molecular weight is 2,000 or more and 80,000 or less.

12. A polymer solution comprising the polymer described in any one of claims 1 to 11.

13. A polymer solution according to claim 12, A polymer solution further comprising a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

14. A polymer solution according to claim 12, A polymer solution used for forming color filters, black matrices, spacers, or partition materials.

15. A polymer according to any one of claims 1 to 11, A photoradical polymerization initiator, Photosensitive resin composition.

16. A cured product formed from the photosensitive resin composition described in claim 15.

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