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

Abstract

To provide a polymer which is excellent in sensitivity and alkali solubility.SOLUTION: A polymer has a structure represented by formula (P). In the formula (P), when molar contents of each structural unit A, B and C contained in the polymer are represented by pt, qt and rt, pt+qt+rt=1, pt is larger than 0, qt is larger than 0, rt is larger than 0, A represents a norbornene-derived structural unit, B represents a maleic acid-derived structural unit having a hydroxy group and two or more (meth)acryloyl groups or a maleic acid-derived structural unit having a hydroxy group and one (meth)acryloyl group, C represents a styrene-derived structural unit, a plurality of A, B and C may be same or different, and a weight average molecular weight of the polymer is 7,000 or more and 50,000 or less.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 reactions and harden upon exposure to light. Color filters, black matrices, spacers, or partition materials are produced by patterning the photosensitive resin composition through exposure and development, followed by hardening. While "increasing sensitivity" may seem like a common challenge for photosensitive resin compositions, the increasing complexity and widespread use of display and imaging devices necessitates even higher levels of sensitivity. Higher sensitivity in a photosensitive resin composition reduces exposure time, improving productivity. Furthermore, photosensitive resin compositions are required to exhibit excellent processability in development processes using alkaline developers. Additionally, the cured product of the photosensitive resin composition is required to possess high transparency. [Means for solving the problem]

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

[0006] According to the present invention, A polymer having a structure represented by formula (P), [ka] 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 [ ]. 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 rt then, p t +q t +r t =1, p t is greater than 0, q t is greater than 0, r t is greater than 0, X is hydrogen or an organic group having 1 to 30 carbon atoms, Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a monofunctional or polyfunctional thiol group-containing compound, A represents a structural unit represented by formula (NB), B comprises at least one structural unit selected from the group consisting of a structural unit represented by formula (1) and a structural unit represented by formula (2), C represents a structural unit represented by formula (ST), when a plurality of A, B or C are present, the plurality of A's, the plurality of B's or the plurality of C's may be the same or different from each other,

Chemical Formula

Chemical Formula

Chemical Formula

Chemical Formula

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

[0008] Furthermore, the present invention provides a photosensitive resin composition comprising the above-mentioned polymer solution and a photopolymerization initiator.

[0009] Furthermore, the present invention provides a cured product of the above-mentioned photosensitive resin composition. [Effects of the Invention]

[0010] The present invention provides a polymer as a resin material for use in a photosensitive resin composition that has good sensitivity, high alkali solubility, and therefore excellent developability, as well as reduced yellowing and therefore high heat resistance to discoloration. [Brief explanation of the drawing]

[0011] [Figure 1] This is a schematic diagram (cross-sectional view) illustrating an example of the structure of a liquid crystal display device and / or a solid-state image sensor. [Figure 2] This is the 13C-NMR chart of raw material polymer 4. [Modes for carrying out the invention]

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

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

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

[0015] [Polymer P] (First embodiment) The polymer of this embodiment (hereinafter referred to as "polymer P") A monomer composition comprising 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) is polymerized in the presence of a monofunctional or bifunctional or more thiol group-containing compound to prepare a raw material polymer (Step I). This polymer is obtained by reacting the raw material polymer with a compound having a hydroxyl group and two or more (meth)acryloyl groups, and / or a compound having a hydroxyl group and one (meth)acryloyl group, in the presence of a basic catalyst (Step II). The polymer P of this embodiment has a weight-average molecular weight of 7,000 to 50,000.

[0016] [ka]

[0017] 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.

[0018] [ka]

[0019] 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.

[0020] [ka]

[0021] 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.

[0022] 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") and / or a compound having a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as a "monofunctional (meth)acrylic compound") used in the above-described step II is introduced. Here, the side chain derived from the polyfunctional / monofunctional (meth)acrylic compound is a residue obtained by removing a hydrogen atom from the hydroxyl group of the polyfunctional / monofunctional (meth)acrylic compound and has at least one (meth)acryloyl group.

[0023] The polymer P of this embodiment contains a thioether group derived from a monofunctional or bifunctional or multi-functional thiol group-containing compound in its structure. Due to the presence of the thioether group, polymer P has excellent sensitivity in photolithography and higher alkali solubility, thus providing a resin cured product with superior developability. Furthermore, the inclusion of the thioether group in polymer P reduces yellowing and provides a resin cured product with excellent transparency.

[0024] Furthermore, the polymer P of this embodiment has structural units derived from norbornene represented by formula (NBm). 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.

[0025] Furthermore, the polymer P in this embodiment has styrene-derived structural units represented by formula (STm). These styrene-derived structural units are also chemically robust. Therefore, polymer P containing these structural units exhibits minimal weight loss and stability when subjected to heat treatment. Thus, photosensitive resin compositions containing polymer P can be suitably used to manufacture films and filters for use in liquid crystal display devices and solid-state image sensors that require heat resistance.

[0026] Furthermore, the polymer P of this embodiment has an organic group containing a (meth)acryloyl group in its side chain. Polymer P may be, for example, a resin having a thioether group and a monofunctional (meth)acryloyl group, a resin having a thioether group and a polyfunctional (meth)acryloyl group, or a resin having a thioether group, a monofunctional (meth)acryloyl group, and a polyfunctional (meth)acryloyl group. Because polymer P has a (meth)acryloyl group, the curing reaction (polymerization reaction) is promoted, and therefore it has excellent sensitivity.

[0027] (Second Embodiment) In the second embodiment, polymer P is A monomer composition containing the monomer represented by the above formula (NBm), the monomer represented by the above formula (STm), and the monomer represented by the above formula (MAm) is polymerized in the presence of a monofunctional or bifunctional or more thiol group-containing compound to prepare a raw material polymer (Step I). This raw material polymer is reacted with a compound having a hydroxyl group and two or more (meth)acryloyl groups, and / or a compound having a hydroxyl group and one (meth)acryloyl group, in the presence of a basic catalyst to prepare a polymer precursor (Step II). This polymer is obtained by treating the polymer precursor with water in the presence of a basic catalyst (Step III).

[0028] 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 polymer precursor obtained in step II, which are ring-opened with water by the treatment in step III (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.

[0029] (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.

[0030] [ka]

[0031] 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, pt +q t +r t = 1, p t It is greater than 0, preferably 0.1 to 0.6, more preferably 0.2 to 0.5, and more preferably 0.25 to 0.45. q t It is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, and more preferably 0.35 to 0.60. r t This value 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. X is either hydrogen or an organic group with 1 to 30 carbon atoms. Y is a 1-30 carbon atom, 1-6 valent organic group derived from monofunctional or bifunctional or multi-functional thiol group-containing compounds. A is a structural unit represented by formula (NB). B includes at least one structural unit selected from the structural units represented by formula (1) and the structural units represented by formula (2). C represents a structural unit expressed by formula (ST). Multiple instances of A, B, or C may be identical or different.

[0032] [ka]

[0033] 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.

[0034] [ka]

[0035] In formula (1), R p R is a group having two or more (meth)acryloyl groups, 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0036] [ka]

[0037] In formula (2), R s R is a group having one (meth)acryloyl group, 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. [ka]

[0038] 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.

[0039] A polymer P having the structure represented by formula (P) may include the structural unit represented by formula (3) as the structural unit B.

[0040] [ka]

[0041] 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.

[0042] A polymer P having the structure represented by formula (P) may include a structural unit B represented by formula (MA). [ka]

[0043] In formula (MA), R 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0044] 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 groups include saturated or unsaturated linear, branched, or cyclic hydrocarbon groups, alkoxy groups, heterocyclic groups, and carboxyl groups. Examples of hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalyl groups, and cycloalkyl groups.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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%.

[0050] In the structural unit represented by the above formula (ST) that constitutes polymer P, R 10 , R 11 and R 12Organic 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.

[0051] 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.

[0052] Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl (k+1 group), tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] Polymer P contains a structural unit containing two or more (meth)acryloyl groups (-C(=O)-CH=CH2) represented by formula (1), a structural unit containing one (meth)acryloyl group represented by formula (2), or a combination thereof. By containing such a structural unit, Polymer P has better sensitivity in exposure processing.

[0058] In formula (1) or formula (2), R 21 and R 22 Examples of the organic group having 1 to 3 carbon atoms that can constitute include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R 21 and R 22 are preferably both hydrogen atoms.

[0059] 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 p By optimizing the number of (meth)acryloyl groups contained in , the sensitivity of Polymer P containing the same in exposure processing can be further improved. In addition, it becomes easier to achieve a higher degree of compatibility between the sensitivity and alkali solubility of Polymer P. Furthermore, the heat resistance of Polymer P can be improved.

[0060] 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 the foregoing. Being such a group tends to facilitate obtaining the various effects described above.

[0061]

Chemical Formula

[0062] In formula (1b), k is 2 or 3, R represents a hydrogen atom or a methyl group, and a plurality of R groups 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 -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and when there are a plurality of X 1 groups, 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'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2 is a (k+1)-valent organic group having 1 to 12 carbon atoms. R is preferably a hydrogen atom from the viewpoint of further improvement in sensitivity (ease of polymerization) and the like. k may be 2 or 3, and is preferably 3 from the viewpoints of availability of raw materials and further improvement in sensitivity.

[0063] X 1 when X is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 when X is an alkylene group having 1 to 6 carbon atoms, X 1 is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and still more preferably -CH2- (methylene group).

[0064] X 1 when X is a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms for X may be linear or branched. the alkylene group having 1 to 6 carbon atoms for X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and still more preferably -CH2-CH2- (ethylene group) or -CH2-CH(CH3)-.

[0065] X 1If ' is an alkylene group having 1 to 6 carbon atoms, then the specific embodiment 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.

[0066] 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 2 The group may include a cyclic structure. Examples of groups including a cyclic structure include groups including an alicyclic structure and groups including a heterocyclic structure (for example, an isocyanuric acid structure).

[0067] [ka]

[0068] 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 4and 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.

[0069] 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.

[0070] [ka]

[0071] 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).

[0072] When polymer P contains structural units represented by formula (1), the proportion of structural units represented by formula (1) in the total structural units of polymer P is preferably 3 to 40 mol%, more preferably 3 to 30 mol%.

[0073] In a structural unit represented by formula (2) that can constitute a polymer (P), 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 contains either or both of the structural units represented by formula (1) and the structural units represented by formula (2), thereby achieving a good balance between sensitivity and developability.

[0074] R S This is a group represented, for example, by the following formula (2a).

[0075] [ka]

[0076] 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.

[0077] X 10 The divalent organic group is more preferably a linear alkylene group having a total of 3 to 6 carbon atoms. 10 Number of carbon atoms (X 10 By appropriately selecting the chain length, the structural unit represented by formula (2) becomes more readily involved in the crosslinking reaction, thereby increasing sensitivity.

[0078] 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.

[0079] When polymer P contains structural units represented by formula (2), the proportion of structural units represented by formula (2) in the total structural units of polymer P is preferably 5 to 30 mol%, more preferably 10 to 20 mol%.

[0080] Furthermore, if polymer P contains both structural units represented by formula (1) and structural units represented by formula (2), the total proportion of structural units represented by formula (1) and structural units represented by formula (2) in polymer P is preferably 5 to 40 mol%, more preferably 10 to 35 mol%, and even more preferably 15 to 30 mol%, based on the total structural units constituting polymer P.

[0081] In the structural units represented by formula (3) that polymer P may contain, R 21 and R 22 Each of these is independently a hydrogen atom or an organic group with 1 to 3 carbon atoms. 21 and R 22 Organic groups having 1 to 3 carbon atoms that can constitute this include methyl, ethyl, n-propyl, and isopropyl groups. 21 and R 22 It is preferable that it is a hydrogen atom.

[0082] [ka]

[0083] Polymer P has high alkali solubility due to containing the structural unit represented by formula (3). As a result, the photosensitive resin composition containing polymer P exhibits excellent developability when subjected to a photolithography method using an alkaline aqueous solution as the developer. When polymer P contains the structural unit represented by formula (3), the proportion of the structural unit represented by formula (3) in the total structural units of polymer P is preferably 1 to 10 mol%, more preferably 2 to 7 mol%.

[0084] In the structural units represented by formula (MA) that polymer P may contain, R 21 and R 22 Each of these is independently a hydrogen atom or an organic group with 1 to 3 carbon atoms. 21 and R 22 Organic groups having 1 to 3 carbon atoms that can constitute this include methyl, ethyl, n-propyl, and isopropyl groups. 21 and R 22 It is preferable that it is a hydrogen atom.

[0085] [ka]

[0086] The structural unit represented by formula (MA) undergoes ring-opening with an alkaline developer to produce two carboxyl groups. Therefore, polymer P has 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 3 to 40 mol%, more preferably 10 to 30 mol%.

[0087] 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.

[0088] 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 This is similar to the organic groups with 1 to 30 carbon atoms that make up the compound.

[0089] 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.

[0090] 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)).

[0091] 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.

[0092] 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.

[0093] 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.

[0094] Examples of monofunctional or bifunctional or multi-functional thiol group-containing compounds that can derive Y in formula (P) include compounds represented by the following chemical formulas (s-1) to (s-21). That is, polymer P contains a C1 to C30 1 to 6-valent organic group (i) derived from monofunctional or bifunctional or multi-functional thiol group-containing compounds as shown below.

[0095] [ka]

[0096]

change

[0097]

change

[0098]

change

[0099]

change

[0100]

change

[0101]

change

[0102]

change

[0103]

change

[0104]

change

[0105]

change

[0106]

change

[0107]

change

[0108]

change

[0109]

change

[0110]

change

[0111]

change

[0112]

change

[0113]

change

[0114]

change

[0115]

change

[0116] 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.

[0117] 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).

[0118] [ka]

[0119] 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, and p 1 +q 1 +r 1 =1, p 2 +q 2 +r 2 =1, p 3 +q 3 +r 3 =1, p 4 +q 4 +r 4 = 1 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.

[0120] 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.

[0121] The weight-average molecular weight Mw of polymer P in this embodiment is 7,000 to 50,000. Preferably, the weight-average molecular weight of polymer P is 7,500 to 45,000, more preferably 8,000 to 40,000, and even more preferably 10,000 to 35,000. By appropriately adjusting the weight-average molecular weight, the sensitivity and solubility in alkaline developers can be adjusted.

[0122] 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 4.2. 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.

[0123] 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).

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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) From the 1H-NMR chart of the polymer, determine the area (integral value) of the peaks corresponding to hydrogen atoms of the carboxyl group and hydrogen atoms near the polymerizable carbon-carbon double bond. From the area obtained in (2)(1), the amount of carboxy groups and the amount of carbon-carbon double bonds are determined from the area of the peak derived from the standard substance. (3) The amount of carboxy groups determined in (2) is converted into an acid value (mgKOH / g). Further, the amount of polymerizable carbon-carbon double bonds determined in (2) is converted into a double bond equivalent (g / mol).

[0129] 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 contained in the (meth)acryloyl groups included in the structural units represented by formulas (1) to (3).

[0130] The content (ratio) of each structural unit contained in polymer P of the present embodiment can be obtained from the charged amount (molar amount) of raw materials during polymer synthesis, the amount of raw materials remaining after synthesis, and peak areas of various spectra (for example, 1 peak areas in 1H-NMR) can be estimated / calculated from such factors.

[0131] [Method for Producing Polymer P] The method for producing polymer P of the present embodiment will be described by taking as an example the case where polymer P has a structure represented by formula (P). Polymer P of the present embodiment is obtained by Step I: a step of preparing a raw material polymer comprising a structural unit represented by formula (NB), a structural unit represented by formula (ST), a structural unit represented by formula (MA), and a 1- to 6-valent organic group (i) having 1 to 30 carbon atoms, and Step II: The polymer can be produced by reacting the raw material polymer obtained in Step I with a compound having a hydroxyl group and two or more (meth)acryloyl groups (a polyfunctional (meth)acrylic compound), and / or a compound having a hydroxyl group and one (meth)acryloyl group (a monofunctional (meth)acrylic compound), in the presence of a basic catalyst, to prepare a polymer P that contains a structural unit represented by formula (NB), a structural unit represented by formula (ST), a C1-C30 C1-C6 valent organic group (i), and a structural unit represented by formula (1) and / or formula (2), and optionally further containing a structural unit represented by formula (MA).

[0132] If polymer P further contains structural units represented by formula (3), the following step III is performed. Step III: A polymer precursor (corresponding to polymer P in Step II) is prepared in Step II, comprising a structural unit represented by formula (NB), a structural unit represented by formula (ST), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA), and then the polymer precursor is treated with water in the presence of a base catalyst to obtain polymer P.

[0133] In step II, when both polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds are used, it is preferable to first react the polyfunctional (meth)acrylic compound with the raw material polymer obtained in step I, and then react the resulting reaction mixture with the monofunctional (meth)acrylic compound.

[0134] 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 13 The 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).

[0135] [ka]

[0136] 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.

[0137] [ka]

[0138] [ka]

[0139] Examples of monofunctional or bifunctional thiol group-containing compounds include, but are not limited to, the compounds represented by the chemical formulas (s-1) to (s-21) above. Monofunctional or bifunctional thiol group-containing compounds may be used individually or in combination of two or more.

[0140] While the polymerization method is not limited, radical polymerization using a radical polymerization initiator is preferred. Examples of polymerization initiators include azo compounds and organic peroxides. Specific examples of azo compounds include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonile) (ABCN). Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Regarding polymerization initiators, one type may be used, or two or more types may be used in combination.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] (Process II) In step II, the raw material polymer obtained in step I is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst. This causes some of the structural units represented by formula (MA) in the raw material polymer to open rings, forming structural units represented by formula (1) and / or formula (2). A polymer precursor is obtained that contains structural units represented by formula (NB), structural units represented by formula (ST), 1-6 valent organic groups (i) having 1-30 carbon atoms, and structural units represented by formula (1) and / or formula (2), and optionally structural units represented by formula (MA). The polymer precursor obtained here can be used as polymer P in this embodiment, but for the sake of explanation, it is referred to as a polymer precursor.

[0145] 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.

[0146] To obtain a polymer precursor containing the structural unit represented by formula (NB), the structural unit represented by formula (ST), and both the structural unit represented by formula (1) and the structural unit represented by formula (2), a polyfunctional (meth)acrylic compound is then added to the above solution. A basic catalyst is then added. The solution is then properly mixed to obtain a homogeneous solution, which yields a polymer precursor containing a structure in which at least the structural unit of formula (NB), the structural unit of formula (ST), and the structural unit of formula (1) are bonded via a C1-C30 C1-C6 valent organic group (i) and 1-6 thioether groups (Step II-i).

[0147] 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 in equation (1c) above. n and R in equation (1d-m) are the same as in equation (1d) above.

[0148] [ka]

[0149] [ka]

[0150] [ka]

[0151] Next, by reacting the polymer obtained in step II-i with a monofunctional (meth)acrylic compound in the presence of a basic catalyst, a polymer precursor can be obtained in which the structural units of formula (NB), formula (ST), formula (1), and formula (2) are bonded via a 1-6 valent organic group (i) having 1-30 carbon atoms and 1-6 thioether groups (step II-ii).

[0152] As a basic catalyst, amine compounds and nitrogen-containing heterocyclic compounds known in the field of organic synthesis can be used as appropriate. For example, amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds can be used as catalysts. The amount of basic catalyst used can be, for example, about 10 to 60 parts by mass per 100 parts by mass of raw material polymer. Note that using an excess of basic catalyst may increase the amount of acid required for neutralization, potentially complicating the purification process.

[0153] By heating the above solution at a temperature of preferably 60-80°C for about 3-9 hours, ring-opening of the structural unit of formula (MA) and formation of the structural unit of formula (1) contained in the raw material polymer are achieved.

[0154] For example, by adding a monofunctional (meth)acrylic compound having a hydroxyl group to the reaction system during the heating process described above, the structural unit represented by formula (2) above can be generated in the structure of polymer P (P).

[0155] Due to steric hindrance and other factors, monofunctional (meth)acrylic compounds containing hydroxyl groups tend to react more readily with the starting polymer than polyfunctional (meth)acrylic compounds containing hydroxyl groups. Therefore, when preparing a polymer precursor having the structural unit of formula (2), it is preferable not to add the monofunctional (meth)acrylic compound containing hydroxyl groups to the reaction system from the beginning, but rather to add it to the reaction system later. Examples of monofunctional (meth)acrylic compounds having a hydroxyl group include compounds represented by the following formulas (2a-m). In equation (2a-m), X 10 The definition of R is the same as that in equation (2a).

[0156] [ka]

[0157] 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.

[0158] When obtaining a polymer precursor containing 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 valents, and either a structural unit represented by formula (1) or a structural unit represented by formula (2), only one of steps II-i or II-ii needs to be carried out after step (I).

[0159] (Process III) When carrying out step III, the polymer precursor obtained in step II is treated with water in the presence of a basic catalyst. Step III causes the structural unit represented by formula (MA) contained in the polymer precursor obtained in step II to undergo ring opening, forming the structural unit represented by formula (3), thereby producing polymer P 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 1-6 valent organic group (i) having 1-30 carbon atoms 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, polymer P further contains the structural unit represented by formula (MA).

[0160] Examples of basic catalysts used in step III include amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds.

[0161] In step III, water is added to the reaction system containing the polymer precursor obtained in step II, and the resulting reaction solution is heated, preferably at 60-80°C for about 0.25-6 hours, causing the structural unit of formula (MA) contained in the polymer to open its ring and generate the structural unit represented by formula (3). The basic catalyst can be the catalyst remaining in the reaction system obtained in step II. Therefore, it is preferable to carry out step III by adding water to the reaction mixture obtained in step II in situ without any post-treatment of the reaction mixture.

[0162] The polymer P of this embodiment can be obtained by the above steps, but from the viewpoint of the effects of the present invention, the following steps may be performed as appropriate to remove unwanted components other than the desired polymer.

[0163] First, the reaction solution, which has been diluted with an organic solvent and to which an acid (such as formic acid) has been added, is vigorously stirred in a separatory funnel for at least 3 minutes. This is then left to stand for at least 30 minutes to separate the organic phase from the aqueous phase, and the aqueous phase is removed. In this way, an organic solution of the polymer is obtained.

[0164] The obtained organic solution of polymer P is purified using either a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the obtained organic solution of polymer P is added to an excess amount of toluene or water to reprecipitation the polymer. The polymer powder obtained by reprecipitation is then washed several more times with toluene or water. Furthermore, in order to remove formic acid and basic catalysts, the obtained polymer powder is washed with deionized water several times (approximately 1 to 3 times). High-purity polymers can be obtained by drying the polymer powder, after washing it with deionized water, at a temperature of, for example, 30-60°C for 16 hours or more. In the liquid-liquid extraction method, water is added to the obtained organic solution of polymer P, and the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This mixture is then allowed to stand for at least 30 minutes to separate the organic phase from the aqueous phase, and the aqueous phase is removed. Water is then added to the organic solution of the polymer after the removal of the aqueous phase, and the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This mixture is then allowed to stand for at least 30 minutes to separate the organic phase from the aqueous phase, and the aqueous phase is removed. In this way, an organic solution of the polymer is obtained. If necessary, the steps of adding water and removing the aqueous phase may be repeated. The obtained polymer organic solution can be concentrated by heating it under reduced pressure using a rotary evaporator, and then diluted by repeating the process of adding a final solvent (such as PGMEA) to obtain a polymer solution dissolved in the final solvent. In addition, further purification by reprecipitation after solvent replacement may be performed.

[0165] Furthermore, the polymer solution may also contain the polyfunctional (meth)acrylic compound and / or monofunctional (meth)acrylic compound used in the synthesis of polymer P. When the polymer solution contains these (meth)acrylic compounds, it is preferable that the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart is 3 to 50%, particularly 5 to 45%, of the peak area of ​​polymer P, and the peak area derived from the monofunctional (meth)acrylic compound is 1 to 50%, particularly 2 to 35%, of the peak area of ​​polymer P. As a result, the photosensitive resin composition containing this polymer solution has good alkali solubility and good sensitivity in photolithography.

[0166] [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.

[0167] (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 II of the production of polymer P, or may be added separately.

[0168] 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).

[0169] [ka]

[0170] [ka]

[0171] [ka]

[0172] k, R, X in equation (1b-p) 1 , X 1 'and X 2 The definition and specific form of are the same as in equation (1b) above. Also, k, R, and X in equation (1c-p) 1 , 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.

[0173] In formulas (1b-p), (1c-p), and (1d-p), Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0174] 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.

[0175] When a polyfunctional (meth)acrylic compound is added to the polymer solution of this embodiment separately from the unreacted polyfunctional (meth)acrylic compound used in the production of polymer P, the amount added can be such that the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less, relative to the peak area of ​​polymer P.

[0176] (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).

[0177] [ka]

[0178] 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.

[0179] 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.

[0180] 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.

[0181] [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.

[0182] [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.

[0183] (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.

[0184] 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.

[0185] (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.

[0186] 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.

[0187] 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.).

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] (Surfactants) The photosensitive resin composition of this embodiment may contain a surfactant, and a nonionic surfactant is preferred as the surfactant.

[0193] The inclusion of a nonionic surfactant improves the coatability of the photosensitive resin composition when applying it to a substrate to obtain a resin film, allowing for the creation of a coating film of uniform thickness. Furthermore, it prevents residue and pattern lifting during the development of the coating film.

[0194] 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.

[0195] (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.

[0196] 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.

[0197] (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.

[0198] 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.

[0199] (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.

[0200] 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.

[0201] Specifically, the crosslinking agents include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene Polyfunctional (meth)acrylates such as oxide-added ditrimethylolpropanetetra(meth)acrylate, ethylene oxide-added pentaerythritoltetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropanetri(meth)acrylate, propylene oxide-added ditrimethylolpropanetetra(meth)acrylate, propylene oxide-added pentaerythritoltetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropanetri(meth)acrylate, ε-caprolactone-added ditrimethylolpropanetetra(meth)acrylate, ε-caprolactone-added pentaerythritoltetra(meth)acrylate, and ε-caprolactone-added dipentaerythritol hexa(meth)acrylate; Polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexanyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexanyl ether; Vinyl ether group-containing (meth)acrylic acid esters such as (meth)acrylate 2-vinyloxyethyl, (meth)acrylate 3-vinyloxypropyl, (meth)acrylate 1-methyl-2-vinyloxyethyl, (meth)acrylate 2-vinyloxypropyl, (meth)acrylate 4-vinyloxybutyl, (meth)acrylate 4-vinyloxycyclohexyl, (meth)acrylate 5-vinyloxypentyl, (meth)acrylate 6-vinyloxyhexyl, (meth)acrylate 4-vinyloxymethylcyclohexylmethyl, (meth)acrylate p-vinyloxymethylphenylmethyl, (meth)acrylate 2-(vinyloxyethoxy)ethyl, (meth)acrylate 2-(vinyloxyethoxyethoxyethoxy)ethyl; Polyfunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether; Allyl group-containing (meth)acrylic acid esters, such as (meth)acrylic acid allyl; Polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl) isocyanurate, tri(methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri(acryloyloxyethyl) isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl) isocyanurate; Polyfunctional allyl group-containing isocyanurates, such as triallyl isocyanurate; Polyfunctional urethane (meth)acrylates obtained by the reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; Examples include:

[0202] 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.

[0203] 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.

[0204] (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.

[0205] [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.

[0206] (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.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211] (exposure) Exposure is typically performed by irradiating a photosensitive resin film with active light through a suitable photomask.

[0212] 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.

[0213] 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.

[0214] (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.

[0215] 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.

[0216] 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.

[0217] 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.

[0218] 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.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] 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.

[0224] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. Further embodiments of the present invention are described below.

[0225] [1] A process to prepare 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, A method for producing a polymer, comprising the step of reacting the raw material polymer with a compound having a hydroxyl group and two or more (meth)acryloyl groups, and / or a compound having a hydroxyl group and one (meth)acryloyl group, in the presence of a basic catalyst, to obtain a polymer, [ka] In the formula (NBm), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2. [ka] In the formula (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. The weight-average molecular weight of the polymer is between 7,000 and 50,000. A method for producing polymers.

[0226] [2] A process of preparing a raw material polymer by polymerizing a monomer composition comprising a monomer represented by the following formula (NBm), a monomer represented by the following formula (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, and / or a compound having a hydroxyl group and one (meth)acryloyl group, in the presence of a basic catalyst, to prepare a polymer precursor. A method for producing a polymer, comprising the step of obtaining a polymer by treating the polymer precursor with water in the presence of a basic catalyst, [ka] In the formula (NBm), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2. [ka] In the formula (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. The weight-average molecular weight of the polymer is between 7,000 and 50,000. A method for producing polymers.

[0227] [3] The method for producing a polymer according to [1] or [2], wherein the monofunctional or bifunctional or more thiol group-containing compound is at least one compound selected from formulas (s-1) to (s-21). [ka]

[0228] [4] A polymer solution comprising a polymer obtained by a polymer manufacturing method described in any of [1] to [3].

[0229] [5] [4] The polymer solution described above, A polymer solution further comprising a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

[0230] A polymer solution as described in [6] [4] or [5], A polymer solution used for forming color filters, black matrices, spacers, or partition materials.

[0231] [7] A polymer obtained by the polymer manufacturing method described in any of [1] to [3], A photoradical polymerization initiator, Photosensitive resin composition.

[0232] A cured product formed from the photosensitive resin composition described in [8] [7]. [Examples]

[0233] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0234] The compounds used in the examples may be indicated by the following abbreviations or trade names. MAN: Maleic anhydride NB:2-Norbornen St: Styrene Vt: Vinyltoluene (4-methylstyrene) • StC:4-carboxystyrene • MEK: Methyl ethyl ketone

[0235] • PEMP: Pentaerythritol tetrakis(3-mercaptopropionate), a thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemicals Co., Ltd.)

[0236] 4-HBA: 4-hydroxybutyl acrylate • A-TMM-3LM-N: A mixture of the following two compounds. Based on gas chromatography measurements, the amount of the compound on the left in the mixture is approximately 57% (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0237] [ka]

[0238] <Synthesis of raw material polymers> (Synthesis of raw material polymer 1) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 602.56 g of a 75% toluene solution of 2-norbornene (equivalent to 451.92 g of 2-norbornene, 4.8 mol), maleic anhydride (MAN, 470.69 g, 4.8 mol), and 2281.74 g of methyl ethyl ketone (MEK) were added and stirred until dissolved. Next, dissolved oxygen was removed from the system by nitrogen bubbling, and the mixture was heated. When the internal temperature reached 80°C, a solution of 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 44.21 g, 0.19 mol) and PEMP (93.82 g, 0.19 mol) dissolved in 193.4 g of MEK was added over 1 hour. The reaction was then continued at 80°C for 7 hours. Finally, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 3686.4 g of methanol to precipitate a white solid. The obtained white solid was then washed with another 3686.4 g of methanol and vacuum-dried at 120°C to obtain 910.1 g of a polymer (raw material polymer 1) comprising structural units derived from 2-norbornene and structural units derived from maleic anhydride. The obtained raw material polymer 1 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 3500, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.62.

[0239] (Confirmation of the thioether structure contained in raw material polymer 1) The elemental PEMP is represented by the following chemical formula. 13 1C-NMR measurements revealed a peak a originating from carbon a at approximately 19.0 ppm and a peak b originating from carbon b at approximately 62.0 ppm.

[0240] [ka]

[0241] Raw material polymer 1 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 raw material polymer 1.

[0242] Also, raw material polymer 1 13 In 1C-NMR measurements, peak a, originating from carbon a, was not observed. Instead, peak c, corresponding to a thioether (RS-R'), appeared around 28 ppm. Since the integral value of peak c is approximately twice that of peak b, it was determined that the raw material polymer 1 has a skeleton containing a thioether group as described below, and the thiol group has disappeared.

[0243] [ka]

[0244] 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, and the presence of sulfur elements in the polymer was confirmed. In addition, the peak derived from PEMP disappeared in the GPC measurement of the reaction solution before methanol addition, confirming that PEMP was incorporated into the raw material polymer 1.

[0245] Elemental analysis revealed that the sulfur content in raw polymer 1 was 2.4 wt%.

[0246] (Synthesis of raw material polymer 2) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 122.40 g (1.18 mol) of styrene, 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 2) comprising structural units derived from styrene and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 14600, 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 2 was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in raw material polymer 2. Furthermore, GPC measurement of the reaction solution did not show a peak for PEMP alone, indicating that no unreacted PEMP remained, thus confirming that PEMP was incorporated into raw material polymer 2. Also, raw material polymer 2 13 1C-NMR measurements confirmed that PEMP was incorporated into the raw material polymer 2.

[0247] (Synthesis of raw material polymer 3) 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 3) comprising structural units derived from 2-norbornene, structural units derived from styrene, and structural units derived from maleic anhydride.

[0248] The obtained raw material polymer 3 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.

[0249] (Synthesis of raw material polymer 4) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 115.49 g of a 75% toluene solution of 2-norbornene (equivalent to 86.62 g of 2-norbornene, 0.920 mol), maleic anhydride (MAN, 112.77 g, 1.150 mol), 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 4) 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, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.30.

[0250] [Structural analysis of raw material polymer 4] The synthesis of raw material polymer 4 begins with the monomer and PEMP dissolved in the solvent at the start of the reaction, after which the reaction proceeds to produce the polymer. Analysis of the reaction solution and the resulting polymer yielded the following results.

[0251] (a) Analysis of the reaction solution GPC analysis of the reaction solution before reprecipitation and purification showed no peak for PEMP alone. This confirmed that no PEMP remained in the reaction solution. Furthermore, GC (gas chromatography) analysis of the reaction solution before reprecipitation and purification showed a decrease in the peaks for norbornene, styrene, and maleic anhydride in the reaction solution after the reaction compared to before the reaction, confirming that norbornene, styrene, and maleic anhydride reacted to form polymers. The measurement conditions for gas chromatography were as follows: ·GC device: GC-2030 (Shimadzu Corporation) • Carrier gas: N2 • Detector: Flame ionization (FID) detector, FID temperature: 300℃ • Column: SH-RXi-1HT, inner diameter 0.25, length 30m, film thickness 0.25μm (Shimadzu GLC Co., Ltd.) • Evaporation chamber temperature: 210℃ Column flow rate: 0.64 mL / min • Column heating conditions: Hold at 50°C for 5 minutes, heat at 20°C / min up to 300°C, hold at 300°C for 10 minutes.

[0252] (b) Analysis of polymers GPC analysis of the polymer after reprecipitation and purification did not reveal peaks for PEMP, norbornene, styrene, or maleic anhydride. This confirmed that no PEMP, norbornene, styrene, or maleic anhydride remained in the polymer. Regarding raw material polymer 4, 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.

[0253] (Confirmation of the structure of raw material polymer 4) 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 4 are as follows: 13 The 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.

[0254] The amount of sulfur in the obtained raw material polymer 4 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 4. In addition, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0255] (Synthesis of raw material polymer 5) Except for using 11.24 g (0.023 mol) of PEMP, the polymer (raw material polymer 5) was prepared in the same manner as raw material polymer 4, and contained structural units derived from norbornene, styrene, and maleic anhydride. 128.1 g of raw material polymer 5 was obtained. The obtained raw material polymer 5 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.

[0256] 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 raw material polymer 5. Also, raw material polymer 5 13 1C-NMR measurements confirmed that PEMP was incorporated into the raw material polymer 5.

[0257] (Synthesis of raw material polymer 6) Except for using 5.62 g (0.012 mol) of PEMP, the preparation was carried out in the same manner as for raw material polymer 4, and 118.0 g of polymer (raw material polymer 6) was obtained, which contained structural units derived from -norbornene, structural units derived from styrene, and structural units derived from maleic anhydride. The obtained raw material polymer 6 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 9,100, and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.36.

[0258] 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 131C-NMR measurements confirmed that PEMP was incorporated into the raw material polymer 6.

[0259] (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 5, 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.

[0260] 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.

[0261] (Synthesis of raw material polymer 8) Except for changing the amount of 2-methyl ethyl ketone to 214.83 g, the synthesis method was the same as for raw material polymer 4 to obtain 210.2 g of polymer (raw material polymer 8) 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 4,400, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.17.

[0262] 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.

[0263] (Synthesis of raw material polymer 9) 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 8 to obtain 225.2 g of polymer (raw material polymer 9) 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.

[0264] The amount of sulfur in the obtained raw material polymer 9 was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the raw material polymer 9. Furthermore, GPC measurement of the reaction solution before methanol addition showed the disappearance of the peak derived from PEMP, confirming that PEMP was incorporated into the polymer.

[0265] (Synthesis of raw material polymer 10) 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, 150.36 g, 1.533 mol), and 662.30 g of methyl ethyl ketone (MEK) were added and stirred until dissolved. Next, dissolved oxygen in the system was removed by nitrogen bubbling, and the system was heated until the internal temperature reached 80°C. Then, a solution of 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 14.41 g, 0.063 mol), styrene 63.88 g (0.613 mol), and PEMP (29.97 g, 0.061 mol) dissolved in 165.6 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 4808.0 g of methanol to precipitate a white solid. The obtained white solid was further washed with 1202.0 g of methanol and then vacuum-dried at 120°C to obtain 300.1 g of a polymer (raw material polymer 10) comprising structural units derived from 2-norbornene, structural units derived from styrene, and structural units derived from maleic anhydride. The obtained raw material polymer 7 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 4,400, and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.65.

[0266] The amount of sulfur in the obtained raw material polymer 10 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur in the raw material polymer 10 was confirmed. 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 10. Also, the raw material polymer 10 13 1C-NMR measurements confirmed that PEMP was incorporated into the raw material polymer 10.

[0267] (Synthesis of raw material polymer 11) Except for replacing styrene with 34.08 g (0.230 mol) of 4-carboxystyrene (StC), 195.1 g of polymer (raw material polymer 11) was obtained in the same manner as raw material polymer 5, comprising structural units derived from 2-norbornene, structural units derived from 4-carboxystyrene, 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 6,600, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.10.

[0268] The sulfur content of the obtained raw material polymer 11 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 11. 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 11. Also, the raw material polymer 11 13 1C-NMR measurements confirmed that PEMP was incorporated into the raw material polymer 11.

[0269] (Synthesis of raw material polymer 12) Except for replacing styrene with 34.08 g (0.230 mol) of 4-carboxystyrene (StC), 185.3 g of polymer (raw material polymer 12) was obtained in the same manner as raw material polymer 4, comprising structural units derived from 2-norbornene, structural units derived from 4-carboxystyrene, 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 4,800, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.12.

[0270] The sulfur content of the obtained raw material polymer 12 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 12. 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 12. Also, the raw material polymer 12 13 1C-NMR measurements confirmed that PEMP was incorporated into the raw material polymer 12.

[0271] (Measurement of physical properties of raw polymer) For raw material polymers 2-12, the amount of each monomer in the reaction solution before and after the reaction was measured by gas chromatography (GC), and the consumption of each monomer was calculated to determine the ratio of each monomer introduced into the raw material polymer. Table 1 below shows the charge ratio of monomers used in the synthesis of the raw material polymer, the ratio of monomers introduced into the raw material polymer, the weight-average molecular weight (Mw) and heterodispersity (Mw / Mn) of the raw material polymer. The measurement conditions for gas chromatography are as follows: ·GC device: GC-2030 (Shimadzu Corporation) • Carrier gas: N2 • Detector: Flame ionization (FID) detector, FID temperature: 300℃ • Column: SH-RXi-1HT, inner diameter 0.25, length 30m, film thickness 0.25μm (Shimadzu GLC Co., Ltd.) • Evaporation chamber temperature: 210℃ Column flow rate: 0.64 mL / min • Column heating conditions: Hold at 50°C for 5 minutes, heat at 20°C / min up to 300°C, hold at 300°C for 10 minutes.

[0272] [Table 1]

[0273] <Synthesis of Polymer P> Polymer P was prepared using the following method.

[0274] (Preparation Example 1) Polymer P1 was prepared by ring-opening the MA units of raw material polymer 1 with a monofunctional (meth)acrylic compound. Details are described below. First, 18.44 g of MEK was added to 10.00 g of raw material polymer 1 (calculated from the amount of raw material polymer 1 used, equivalent to 0.052 moles of MA) to prepare a solution. Next, 9.38 g (0.065 moles) of 4-HBA was added to this solution, followed by 3.00 g (0.030 moles) of triethylamine. The mixture was reacted at 70°C for 6 hours to prepare the reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase. The polymer was then purified by the reprecipitation method described below. • Reprecipitation method: The polymer was reprecipitation with an excess amount of water. The polymer powder obtained by reprecipitation was washed twice with an excess amount of water. The resulting reaction product was dried at 40°C for 12 hours. Based on the above, 8.7 g of polymer P1 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 1 with 4-HBA. The obtained polymer P1 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P1 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P1 did not contain any unreacted monofunctional (meth)acrylic compound.

[0275] (Preparation Example 2) Polymer P2 was prepared by ring-opening the MA units of raw material polymer 1 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. Details are described below. First, a solution was prepared by adding 99.93g of MEK to 60.00g of raw material polymer 1 (calculated from the amount of raw material polymer 1 used, equivalent to 0.312 moles of MA). Next, 77.49g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 56.27g (0.390 moles) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours to prepare the reaction solution. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70°C for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase. Further liquid-liquid extraction and subsequent solvent replacement were performed according to the following procedure. • Liquid-liquid extraction: The reaction solution was diluted with MEK, then water was added and treated to remove the aqueous phase from the reaction solution, and the same procedure was repeated once more. • Solvent Replacement: The resulting reaction mixture was subjected to solvent removal under reduced pressure at 50°C using a rotary evaporator. The solvent removal process was stopped when the solid content of the polymer solution was confirmed to be 27±2% by mass, as measured by a heat-drying moisture meter. Then, PGMEA was added to bring the solid content to 18% by mass and mixed until homogeneous. The same procedure was repeated two more times: solvent removal under reduced pressure at 50°C, adjusting the solid content to 27±2% by mass as measured by a heat-drying moisture meter, then adding PGMEA to bring the solid content to 18% by mass and mixing until homogeneous. Subsequently, solvent removal or the addition of PGMEA was performed, and the mixture was stirred until homogeneous, to bring the solid content to 30±3% by mass. Through these operations, the solvent used in the reaction was removed and replaced with PGMEA. Further purification was then carried out according to the following procedure. The polymer was reprecipitated with an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. The polymer powder, after being washed twice as described above, was washed three times with an excess amount of water. The resulting reaction product was dried at 40°C for 12 hours. Based on the above, polymer P2 was prepared by ring-opening the MA units of raw material polymer 1 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P2 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P2 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P2 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P2 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0276] (Preparation Example 3) A resin mixture (polymer solution P3) containing polymer P3, obtained by ring-opening the MA units of raw material polymer 1 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared. Details are described below. First, a solution was prepared by adding 99.93g of MEK to 60.00g of raw material polymer 1 (calculated from the amount of raw material polymer 1 used, equivalent to 0.312 moles of MA). Next, 77.49g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 56.27g (0.390 moles) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours to prepare the reaction solution. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70°C for 2 hours. The resulting reaction solution was diluted with MEK, and the aqueous phase was removed from the reaction solution by treating it with aqueous formic acid and aqueous citric acid solutions. Further liquid-liquid extraction and subsequent solvent replacement were performed according to the following procedure. • Liquid-liquid extraction: The reaction solution was diluted with MEK, then water was added and treated to remove the aqueous phase from the reaction solution, and the same procedure was repeated once more. • Solvent Replacement: The solvent was removed from the resulting reaction mixture under reduced pressure at 50°C using a rotary evaporator. The solvent removal operation was stopped when the solid content concentration of the polymer solution was confirmed to be 27±2 mass% by measurement using a heat-drying type moisture meter. Then, PGMEA was added to bring the solid content concentration to 18 mass% and mixed until homogeneous. The same procedure was repeated two more times, removing the solvent under reduced pressure at 50°C, adjusting the solid content concentration to 27±2 mass% by measurement using a heat-drying type moisture meter, and then adding PGMEA to bring the solid content concentration to 18 mass% and mixing until homogeneous. After that, the solvent was removed or PGMEA was added and stirred until homogeneous to bring the solid content concentration to 30±3 mass%. Through these operations, the solvent used in the reaction was removed and replaced with PGMEA.

[0277] As a result, polymer P3 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 1 with A-TMM-3LM-N, 4-HBA, and water, and a resin mixture (polymer solution P3) containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained. The obtained polymer solution P3 was analyzed by gel permeation chromatography to determine the amounts of polymer P3, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds in the solution, as well as the weight-average molecular weight and polydispersity of polymer P3. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P3 in the gel permeation chromatography (GPC) chart of the resin mixture. The measurement conditions for gel permeation chromatography are as follows: The GPC measurement device used was the HLC-8320GPC EcoSEC from Tosoh Corporation. The column temperature was set to 40.0°C and the pump flow rate to 0.350 mL / min. • Peak position (holding time) Polymer P3: Peaks detected before 20 minutes (peaks with shorter retention times and higher molecular weights than A-TMM-3LM-N and 4-HBA) A-TMM-3LM-N: Total of two peaks at 20.0-20.6 minutes and 20.6-21.5 minutes. 4-HBA: 21.7~22.4 minutes • Measurement conditions: Analysis was performed using a differential refractive index detector (RI detector).

[0278] (Preparation Example 4) Polymer P4 was prepared in the same manner as in Preparation Example 1, except that 10.00 g of raw material polymer 2 (0.049 moles in MA equivalent, calculated from the amount of raw material polymer 2 used) was used instead of raw material polymer 1, by ring-opening the MA units of raw material polymer 2 with a monofunctional (meth)acrylic compound. The obtained polymer P4 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P4 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P4 did not contain any unreacted monofunctional (meth)acrylic compound.

[0279] (Preparation Example 5) Except for using 60.00g of raw material polymer 2 (0.297 moles in MA equivalent calculated from the amount of raw material polymer 2 used) instead of raw material polymer 1, the same procedure as in Preparation Example 3 was used to prepare a resin mixture (polymer solution P5) containing the MA units of raw material polymer 2, a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and polymer P5 whose rings were opened with water. The obtained polymer solution P5 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amounts of polymer P5, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P5. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P5 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0280] (Preparation Example 6) Polymer P6 was prepared in the same manner as in Preparation Example 1, except that 10.00 g of raw material polymer 3 (0.051 moles in MA equivalent, calculated from the amount of raw material polymer 3 used) was used instead of raw material polymer 1, and the MA units of raw material polymer 3 were ring-opened with a monofunctional (meth)acrylic compound. The obtained polymer P6 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P6 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P6 did not contain any unreacted monofunctional (meth)acrylic compound.

[0281] (Preparation Example 7) Polymer P7 was prepared in the same manner as in Preparation Example 1, except that 10.00 g of raw material polymer 4 (0.051 moles in MA equivalent, calculated from the amount of raw material polymer 4 used) was used instead of raw material polymer 1, by ring-opening the MA units of raw material polymer 4 with a monofunctional (meth)acrylic compound. The obtained polymer P7 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer 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.

[0282] (Preparation Example 8) Polymer P8 was prepared in the same manner as in Preparation Example 1, 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 1, and the MA units of raw material polymer 5 were ring-opened with a monofunctional (meth)acrylic compound. The obtained polymer P8 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. 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.

[0283] (Preparation Example 9) Except for using 60.00g of raw material polymer 4 (0.309 moles in MA equivalent, calculated from the amount of raw material polymer 4 used) instead of raw material polymer 1, polymer P9 was prepared in the same manner as in Preparation Example 2 by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P9 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer 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.

[0284] (Preparation Example 10) A resin mixture (polymer solution P10) containing polymer P10, obtained by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 3, except that 60.00 g of raw material polymer 4 (0.309 moles in MA equivalent, calculated from the amount of raw material polymer 4 used) was used instead of raw material polymer 1.

[0285] The obtained polymer solution P10 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amounts of polymer P10, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P10. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P10 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0286] (Preparation Example 11) A resin mixture (polymer solution P11) containing polymer P11, obtained by ring-opening the MA units of raw material polymer 5 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 3, except that 60.00 g of raw material polymer 5 (0.309 moles in MA equivalent, calculated from the amount of raw material polymer 5 used) was used instead of raw material polymer 1. The obtained polymer solution P11 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amounts of polymer P11, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the polymer solution P11, as well as the weight-average molecular weight and polydispersity of polymer P11. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P11 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0287] (Preparation Example 12) A resin mixture (polymer solution P12) containing polymer P12, obtained by ring-opening the MA units of the raw material polymer 6 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 3, except that 60.00 g of raw material polymer 6 (0.309 moles in MA equivalent, calculated from the amount of raw material polymer 6 used) was used instead of raw material polymer 1. The obtained polymer solution P12 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amounts of polymer P12, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the polymer solution P12, as well as the weight-average molecular weight and polydispersity of polymer P12. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P12 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0288] (Preparation Example 13) Except for using 60.00g of raw material polymer 7 (0.306 moles in MA equivalent, calculated from the amount of raw material polymer 7 used) instead of raw material polymer 1, polymer P13 was prepared in the same manner as in Preparation Example 2 by ring-opening the MA units of raw material polymer 7 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P13 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P13 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P13 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P13 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0289] (Preparation Example 14) A resin mixture (polymer solution P14) containing polymer P14, obtained by ring-opening the MA units of raw material polymer 7 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 3, except that 60.00 g of raw material polymer 7 (0.306 moles in MA equivalent, calculated from the amount of raw material polymer 7 used) was used instead of raw material polymer 1. The obtained polymer solution P14 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amounts of polymer P14, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P14. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P14 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0290] (Preparation Example 15) Polymer P15 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. In detail, polymer P15 was prepared in the same manner as in Preparation Example 13, except that 6.00 g (0.059 mol) of triethylamine was used, by ring-opening the structural units derived from maleic anhydride in the raw material polymer 7 with A-TMM-3LM-N, 4-HBA, and water. The obtained polymer P15 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P15 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P15 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 131C-NMR measurements confirmed that polymer P15 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0291] (Preparation Example 16) A resin mixture (polymer solution P16) containing polymer P16, obtained by ring-opening the MA units of raw material polymer 7 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared. In detail, except that 6.00 g (0.059 mol) of triethylamine was used, the procedure was the same as in Preparation Example 14 to obtain polymer P16, in which the structural units derived from maleic anhydride in the raw material polymer 7 were ring-opened with A-TMM-3LM-N, 4-HBA, and water, and a resin mixture (polymer solution P16) containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA. The obtained polymer solution P16 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amounts of polymer P16, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P16. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P16 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0292] (Preparation Example 17) A resin mixture (polymer solution P17) containing polymer P17, obtained by ring-opening the MA units of raw material polymer 8 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared. Details are described below. First, a solution was prepared by adding 99.93g of MEK to 60.00g of raw material polymer 8 (calculated from the amount of raw material polymer 1 used, equivalent to 0.309 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 was performed by diluting the reaction solution with MEK again, then adding a water / methanol mixed solvent and treating the solution to remove the aqueous phase. This process was then repeated once more. Finally, solvent replacement was carried out using the same procedure as in Preparation Example 3. As a result, polymer P17 was obtained by ring-opening the structural units derived from maleic anhydride in the raw material polymer 8 with A-TMM-3LM-N, 4-HBA, and water, and a resin mixture (polymer solution P17) containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained.

[0293] The obtained polymer solution P17 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amounts of polymer P17, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P17. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P17 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0294] (Preparation Example 18) A resin mixture (polymer solution P18) containing polymer P18, obtained by ring-opening the MA units of raw material polymer 8 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared. Details are described below. First, 60.00 g of raw material polymer 8 (calculated from the amount of raw material polymer 1 used, equivalent to 0.312 moles in MA) was mixed with 99.93 g of MEK to prepare a solution. Next, 77.49 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 56.27 g (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, 24.00 g (1.336 mol) of water was added to the reaction solution, and the mixture was reacted at 70°C for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase. Further liquid-liquid extraction was performed by diluting the reaction solution with MEK again, then adding a water / methanol mixed solvent and treating the solution to remove the aqueous phase. This process was then repeated once more. Finally, solvent replacement was carried out using the same procedure as in Preparation Example 3. As a result, polymer P18 was obtained by ring-opening the structural units derived from maleic anhydride in the raw material polymer 8 with A-TMM-3LM-N, 4-HBA, and water, and a resin mixture (polymer solution P18) containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained.

[0295] The obtained polymer solution P18 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amounts of polymer P18, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P18. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P18 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0296] (Preparation Example 19) A resin mixture (polymer solution P19) containing polymer P19, obtained by ring-opening the MA units of raw material polymer 9 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 17, except that 60.00 g of raw material polymer 9 (0.305 moles in MA equivalent, calculated from the amount of raw material polymer 9 used) was used instead of raw material polymer 8. The obtained polymer solution P19 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amounts of polymer P19, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P14. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P19 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0297] (Preparation Example 20) A resin mixture (polymer solution P20) containing polymer P20, obtained by ring-opening the MA units of raw material polymer 10 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 17, except that 60.00 g of raw material polymer 10 (0.306 moles in MA equivalent, calculated from the amount of raw material polymer 10 used) was used instead of raw material polymer 8. The obtained polymer solution P20 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amounts of polymer P20, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P20. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P20 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0298] (Preparation Example 21) Polymer P21 was prepared in the same manner as in Preparation Example 1, except that 10.00 g of raw material polymer 11 (0.049 moles in MA equivalent calculated from the amount of raw material polymer 11 used) was used instead of raw material polymer 1, and the MA units of raw material polymer 11 were ring-opened with a monofunctional (meth)acrylic compound. The obtained polymer P21 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P21 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P21 did not contain any unreacted monofunctional (meth)acrylic compound.

[0299] (Preparation Example 22) A resin mixture (polymer solution P22) containing polymer P22, obtained by ring-opening the MA units of raw material polymer 12 with water, was prepared in the same manner as in Preparation Example 17, except that 60.00 g of raw material polymer 12 (0.295 moles in MA equivalent calculated from the amount of raw material polymer 12 used) was used instead of raw material polymer 8. The obtained polymer solution P22 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amounts of polymer P22, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P22. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P22 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0300] (Preparation Example 23) Polymer P23 was prepared by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound and water. Details are described below. First, a solution was prepared by adding 99.93g of MEK to 60.00g of raw polymer 4 (calculated as 0.234 moles of MA based on the amount of raw polymer 4 used). Next, 77.49g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70°C for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase. Further liquid-liquid extraction as described in Preparation Example 2 was performed, followed by solvent replacement. Subsequently, the product was further purified by the same reprecipitation method as in Preparation Example 2. Based on the above, polymer P23 was prepared by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound and water. The obtained polymer P23 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P23 confirmed the disappearance of the peak of the polyfunctional (meth)acrylic compound used. This confirmed that the obtained polymer P23 did not contain any unreacted polyfunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P23 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N and water.

[0301] (Preparation Example 24) A resin mixture (polymer solution P24) containing polymer P24, obtained by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound and water, was prepared. Details are described below. First, a solution was prepared by adding 99.93g of MEK to 60.00g of raw polymer 4 (calculated as 0.234 moles of MA based on the amount of raw polymer 4 used). Next, 77.49g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70°C for 2 hours. The resulting reaction solution was diluted with MEK, and the aqueous phase was removed from the reaction solution by treating it with aqueous formic acid and aqueous citric acid solutions. Further liquid-liquid extraction and solvent replacement were performed in the same manner as in Preparation Example 3. This allowed us to prepare a resin mixture (polymer solution P24) containing polymer P24, which is obtained by ring-opening the MA units of raw material polymer 4 with a trifunctional (meth)acrylic compound and water.

[0302] The obtained polymer solution P24 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 3 to determine the amount of polymer P24 and free polyfunctional (meth)acrylic compound contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P24. The results are shown in Table 2. The amount of free (meth)acrylic compound is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compound relative to the peak area of ​​polymer P24 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0303] (Evaluation of physical properties) The acid value and double bond equivalent of each polymer P prepared in Preparation Examples 4, 6-9, 13, 15, and 21 were measured by the method described below.

[0304] (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 1. An acid value of 50 gKOH / g or higher indicates that the polymer contains sufficient carboxyl groups necessary for adequate development.

[0305] (double bond equivalent) The double bond equivalents of the polymer were measured by the following method. Similar to the above method for measuring acid value, 1 ¹H-NMR measurements were performed. The amount of acryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal originating from acryloyl groups (5.6-5.8 ppm, 3H) and the signal of the phenyl group of the internal standard (8.1 ppm, 4H) in the obtained spectral chart. The amount of methacryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal originating from methacryloyl groups (5.6-5.8 ppm, 2H) and the signal of the phenyl group of the internal standard (8.1 ppm, 4H). Here, the signal originating from methacryloyl groups at 6.0-6.1 ppm was negligible and overlapped with the signal of acryloyl groups, so it was calculated as the signal of acryloyl groups. The amount of double bonds (mol / g) was calculated from the sum of the calculated amount of acryloyl groups (mol / g) and methacryloyl groups (mol / g) in the polymer, and the double bond equivalent (g / mol) was calculated from the double bond amount. The results are shown in Table 2. A smaller double bond equivalent value indicates a larger amount of C=C double bonds per unit mass of polymer. Also 1 Table 2 shows the proportion of structures obtained by ring-opening with 4-HBA in the overall structure of polymers P6-P8 and P21, which were obtained in preparation examples 6-8 and 21, as calculated from 1H-NMR.

[0306] [Table 2] [Table 3]

[0307] (Examples 1-17, Comparative Examples 1-7) In each example and comparative example, a resin composition was prepared and evaluated for the following items. <Rating> [Alkali dissolution rate of resin compositions] Polymers P1, P2, P4, P6-P9, P13, P15, P21, and P23 obtained in Preparation Examples 1, 2, 4, 6-9, 13, 15, 21, and 23 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1, 2, 4, 6-9, 13, 15, 21, and 23 with a solid content concentration of 30% by mass. Next, resin compositions 3, 5, 10-12, 14, 16-20, 22, and 24, consisting of polymer solutions P3, P5, P10-P12, P14, P16-P20, P22, and P24 obtained from the above resin compositions 1, 2, 4, 6-9, 13, 15, 21, 23, or preparation examples 3, 5, 10-12, 14, 16-20, 22, and 24, were spin-coated onto a wafer, the PGMEA was dried, and then the film was pre-baked at 100°C for 2 minutes to produce a resin film with a thickness of approximately 2 μm. The resin film, along with the wafer, was immersed in a 2% sodium carbonate aqueous solution at 23°C, and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and then dividing the film thickness by that time. The results are shown in Table 3. If the alkali dissolution rate is 40 nm / s or higher, it can be used without problems as a photosensitive material; if it is 100 nm / s or higher, it can be considered to have good developability; if it is 500 nm / s or higher, it can be considered to have even better developability; and if it is 1000 nm / s or higher, it can be considered to have particularly good developability.

[0308] [Sensitivity evaluation of photosensitive resin composition 1 (exposure amount at which the residual film rate is 90% or more)] First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solids content concentration was 30% by mass. Polymers P1, P2, P4, P6-P9, P13, P15, P21, P23 (polymers P from Preparation Examples 1, 2, 4, 6-9, 13, 15, 21, and 23, respectively) or resin compositions 3, 5, 10-12, 14, 16-20, 22, and 24 (polymer solutions P3, P5, P10-P12, P14, P16-P20, P22, and P24 from Preparation Examples 3, 5, 10-12, 14, 16-20, 22, and 24, respectively): 100 parts by mass (Here, for resin compositions 3, 5, 10-12, 14, 16-20, 22, and 24, the total amount of solids (polymers P3, P5, P10-P12, P14, P16-P20, P22, P24) and polyfunctional (meth)acrylic compounds was weighed to 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

[0309] The obtained photosensitive resin composition was rotary coated onto a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds to obtain a thin film A with a thickness of approximately 3.0 μm (±0.3 μm). This thin film A is subjected to a 100 mJ / cm² radiation dose using a Canon g+h+i-ray mask aligner (PLA-501F) via a photomask with a light-shielding rate of 1-100%. 2 The g+h+i line was exposed with the specified exposure dose. After exposure, the thin film is developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (wafer immersion) to achieve a radiation level of 1-100 mJ / cm². 2 Thin films B were obtained by exposing and developing them at each exposure level. The residual film percentage was calculated from the film thicknesses of thin films A and B obtained by the above method using the following formula. Residual film percentage (%) = (Film thickness of thin film B at each exposure dose / Film thickness of thin film A) × 100 The exposure dose at which a residual film rate of 90% or more was determined as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. The exposure dose at which a residual film rate of 90% or more was 15 mJ / cm² 2 If the following conditions are met, it can be used without problems as a photosensitive composition, and the concentration is 12 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.

[0310] [Sensitivity evaluation of photosensitive resin composition 2 (residual film rate after exposure at low exposure)] (5mJ / cm 2 (Percentage of residual film at the exposure level) The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above was rotary coated onto a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds to obtain a thin film A with a thickness of 3.0 μm (±0.3 μm). This thin film A is subjected to a photomask with a light-shielding rate of 1-100% using a Canon g+h+i-ray mask aligner (PLA-501F) at a rate of 5 mJ / cm². 2 The g+h+i line was exposed with the specified exposure dose. After exposure, the thin film was developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (immersed together with the wafer) to obtain thin film B. The residual film percentage was calculated from the film thicknesses of thin films A and B obtained by the above method using the following formula. Residual film percentage (%) = (Film thickness of thin film B at each exposure dose / Film thickness of thin film A) × 100 The results are shown in Table 3. 5 mJ / cm 2 The higher the residual film ratio at a given exposure level, the more easily the film hardens at lower exposure levels, and the better the sensitivity can be considered to be.

[0311] (10mJ / cm 2 (Percentage of residual film at the exposure level) The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above was rotary coated onto a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds to obtain a thin film A with a thickness of 3.0 μm (±0.3 μm). This thin film A is subjected to a 10 mJ / cm² radiation dose using a Canon g+h+i-ray mask aligner (PLA-501F) via a photomask with a light-shielding rate of 1-100%. 2 The g+h+i line was exposed with the specified exposure dose. After exposure, the thin film was developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (immersed together with the wafer) to obtain thin film B. The residual film percentage was calculated from the film thicknesses of thin films A and B obtained by the above method using the following formula. Residual film percentage (%) = (Film thickness of thin film B at each exposure dose / Film thickness of thin film A) × 100 The results are shown in Table 3. 10 mJ / cm 2 The higher the residual film ratio at a given exposure level, the more easily the film hardens at lower exposure levels, and the better the sensitivity can be considered to be.

[0312] [Alkaline dissolution rate of photosensitive resin composition (2.0% by mass sodium carbonate aqueous solution)] The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above was spin-coated onto a wafer, the PGMEA was dried, and then a resin film with a thickness of approximately 2 μm was fabricated by pre-baking at a temperature of 100°C for 2 minutes. The resin film, along with the wafer, was immersed in a 2% sodium carbonate aqueous solution at 23°C, and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and then dividing the film thickness by that time. The results are shown in Table 3. If the alkali dissolution rate is 100 nm / s or higher, it can be used without problems as a photosensitive material; if it is 200 nm / s or higher, it can be considered to have good developability; if it is 500 nm / s or higher, it can be considered to have even better developability; and if it is 700 nm / s or higher, it can be considered to have particularly good developability.

[0313] [Yellow Index] The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above was rotary coated onto Eagle XG glass (Corning, 0.5 mm thick) and baked on a hot plate at 100°C for 120 seconds to obtain a thin film with a thickness of approximately 3.0 μm (±0.1 μm). This thin film was subjected to a 100 mJ / cm² radiation dose using a Canon g+h+i-line mask aligner (PLA-600F). 2 The g+h+i line was exposed with the specified exposure dose. After exposure, the thin film is developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (wafer immersion) to achieve a radiation level of 100 mJ / cm². 2 A thin film was obtained by exposing and developing it with the specified exposure level. The thin film was heat-treated at 230°C for 30 minutes under air conditions. After the thin film was cooled under air conditions at room temperature, it was heat-treated again at 230°C for 30 minutes under air conditions. The same procedure was repeated, and the heat treatment under air 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, and if it is 0.90 or less, it can be considered to have particularly good resistance.

[0314] The results of the developability and sensitivity evaluations are shown in Table 3.

[0315] [Table 4] [Table 5]

[0316] The photosensitive resin compositions of Comparative Examples 1-3, in which polymer P does not contain styrene-derived structural units, had low YI values, but required high exposure levels to achieve a residual film rate of 90% or more, resulting in inferior sensitivity compared to the photosensitive resin compositions of the Examples. The photosensitive resin compositions of Comparative Examples 4 and 5, in which polymer P does not contain norbornene-derived structural units, exhibited superior sensitivity, but had high YI values ​​and inferior heat discoloration resistance. The photosensitive resin composition of Comparative Example 6, in which polymer P does not contain structures derived from thiol group-containing compounds (PEMP), exhibited superior sensitivity, but had high YI values ​​and inferior heat discoloration resistance. The photosensitive resin composition of Comparative Example 7, in which the weight-average molecular weight of polymer P is less than 7,000, had a low YI value, but required high exposure levels to achieve a residual film rate of 90% or more, resulting in inferior sensitivity. Example 1, in which polymer P contains structural units derived from norbornene, styrene, and a thiol group-containing compound (PEMP), and has a ring-opened structure with a monofunctional (meth)acrylic compound, and has a weight-average molecular weight of 7,000 or more, exhibited a low YI, a low exposure dose at which a residual film rate of 90% or more was achieved, and therefore excellent sensitivity. The photosensitive resin compositions of Examples 2-13 and 15-17, in which polymer P contains structural units derived from norbornene, styrene, vinyltoluene, or carboxystyrene, and a thiol group-containing compound (PEMP), and has a ring-opened structure with a polyfunctional (meth)acrylic compound, and have a weight-average molecular weight of 7,000 or more, exhibited a low YI, an even lower exposure dose at which a residual film rate of 90% or more was achieved, and were particularly excellent in sensitivity. The photosensitive resin compositions of Examples 2-13 and 15, in which polymer P contains structural units derived from norbornene, styrene, vinyltoluene, or carboxystyrene, and structures derived from thiol group-containing compounds (PEMP), and has a ring-opened structure with polyfunctional and monofunctional (meth)acrylic compounds, and has a weight-average molecular weight of 7,000 or more, exhibited low YI, even lower exposure levels for a residual film rate of 90% or more, and were particularly superior in sensitivity. Furthermore, in Examples 3, 4, 5, 7, and 9-13 and 15, which contained free polyfunctional / monofunctional (meth)acrylic compounds in the composition, the YI was 5 mJ / cm³. 2 The residual film ratio was high at the exposure level, and the sensitivity was particularly excellent. The photosensitive resin composition of Example 14, in which polymer P contains structural units derived from norbornene, structural units derived from carboxytoluene, and structures derived from a thiol group-containing compound (PEMP), and has a ring-opened structure with a monofunctional (meth)acrylic compound, and has a weight-average molecular weight of 7,000 or more, exhibited low YI, a low exposure amount resulting in a residual film rate of 90% or more, and excellent sensitivity. The photosensitive resin compositions of Examples 14 and 15, in which polymer P contains structural units derived from norbornene, structural units derived from styrene, and structures derived from thiol group-containing compounds (PEMP), and has a ring-opened structure with a polyfunctional (meth)acrylic compound, and has a weight-average molecular weight of 7,000 or more, exhibited low YI, low exposure levels resulting in a residual film rate of 90% or more, and excellent sensitivity.

[0317] <Making color filters / spacers> To the photosensitive resin compositions prepared in Examples 1 to 17, 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.

[0318] <Creation of Black Matrix / Black Bank / Black Spacer> To the photosensitive resin compositions prepared in Examples 1 to 17, 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]

[0319] 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 respective structural units A, B and C contained in the polymer are respectively p ｔ , q ｔ and r ｔ , 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 at least one structural unit selected from the structural units represented by formula (1) and the structural units represented by formula (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), R ｐ R is a group having two or more (meth)acryloyl groups, ２１ and R ２２ Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. 【Chemistry 4】 In formula (2), R ｓ R is a group having one (meth)acryloyl group. ２１ and R ２２ Each of these is independently 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 These are, independently, a hydrogen atom and an organic group having 1 to 30 carbon atoms. The weight-average molecular weight of the polymer is 7,000 or more and 50,000 or less. polymer.

2. The polymer according to claim 1, The aforementioned B further includes a structural unit represented by formula (3), 【Transformation 6】 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.

3. A polymer according to claim 1 or 2, The aforementioned B further includes a structural unit represented by formula (MA), 【Transformation 7】 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.

4. A polymer according to any one of claims 1 to 3, The aforementioned B includes a structural unit represented by formula (1), R in formula (1) 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), 【Transformation 8】 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 9】 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 10】 In formula (1d), n is an integer between 2 and 5. R is independently either a hydrogen atom or a methyl group. polymer.

5. A polymer according to any one of claims 1 to 4, The aforementioned B includes a structural unit represented by formula (2), R in formula (2) ｓ This is a base represented by formula (2a), 【Chemistry 11】 In formula (2a), X １０ R is a divalent organic group, and R is either a hydrogen atom or a methyl group. polymer.

6. A polymer according to any one of claims 1 to 5, 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.

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

8. The polymer solution according to claim 7, A polymer solution further comprising a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

9. A polymer solution according to claim 7 or 8, A polymer solution used for forming color filters, black matrices, spacers, or partition materials.

10. A polymer according to any one of claims 1 to 6, A photoradical polymerization initiator, Photosensitive resin composition.

11. A cured product formed from the photosensitive resin composition described in claim 10.

Images