Polymers, polymer solutions and photosensitive resin compositions

Abstract

The polymer of the present application is represented by the following general formula (P). In general formula (P), Y is a 1 to 6-valent organic group having 1 or more and 30 or less carbon atoms derived from a thiol group-containing compound having 2 or more functional groups, Chain contains a structural unit represented by the following general formula (AE-1) and a structural unit represented by the following general formula (AE-2), and n is an integer of 1 to 6.

Description

Technical Field

[0001] This invention relates to a polymer, a polymer solution, and a photosensitive resin composition. Background Technology

[0002] Liquid crystal display devices or solid-state imaging elements typically include color filters or black matrices. Photosensitive resin compositions are frequently used in the formation of color filters or black matrices.

[0003] For example, claim 1 of Patent Document 1 describes a photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, wherein the alkali-soluble resin has at least one group containing an acidic group in its side chain and two or more different polymerizable unsaturated groups. Furthermore, embodiments of Patent Document 1 describe the synthesis of a methacrylic acid / allyl methacrylate / glycidyl adduct as an alkali-soluble resin and its use in preparing the photosensitive resin composition.

[0004] Patent Document 2 discloses a resin composition comprising a resin, a polyfunctional (meth)acrylate monoester containing hydroxyl groups, and a solvent. The resin contains epoxy groups and acid groups. The resin composition is characterized in that, relative to 1 mole of acid group in the resin containing epoxy groups and acid groups, the epoxy group is 0.5 to 3.0 moles.

[0005] Patent Document 3 discloses a method for manufacturing a polymer, which includes a step of reacting an epoxy-containing compound with a precursor polymer whose maleic anhydride site has been ring-opened. Glycidyl methacrylate is described as an epoxy-containing compound.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent document 1: International Publication No. 2012 / 147706.

[0009] Patent Document 2: International Publication No. 2016 / 103844.

[0010] Patent document 3: International Publication No. 2017 / 154439. Summary of the Invention

[0011] The technical problem to be solved by the invention

[0012] The photosensitive resin composition used to form color filters or black matrices uses a polymer having the property of undergoing a polymerization reaction and curing by means of light. The color filters or black matrices are manufactured by patterning the photosensitive resin composition using exposure and development, followed by curing.

[0013] In photosensitive resin compositions, "high sensitivity" is considered a common challenge, with increasing demands for higher levels of sensitivity arising from the increasing complexity and prevalence of display and imaging devices. Higher sensitivity (better sensitivity) in a photosensitive resin composition results in shorter exposure times, thereby improving productivity.

[0014] Furthermore, the cured product of the photosensitive resin composition needs to be free from yellowing and have excellent transparency or heat resistance to discoloration. In addition, when a pattern is formed by coating the photosensitive resin composition onto a substrate or the like and exposing and developing the resulting coating film, excellent adhesion to the substrate or the like is required from the viewpoint of product yield or product reliability.

[0015] In patent documents 1-3, there is room for improvement in these characteristics.

[0016] means for solving technical problems

[0017] The inventors of this invention discovered that by modifying the polymer used in the photosensitive resin composition, a resin cured product with good sensitivity, high heat resistance and colorfastness that inhibits yellowing, and excellent adhesion to the substrate can be obtained, thereby achieving the present invention.

[0018] That is, the present invention can be shown as follows.

[0019] According to the present invention, it is possible to provide a polymer, wherein the polymer is represented by the following general formula (P).

[0020]

[0021] In general formula (P), Y is an organogroup with 1 to 30 carbon atoms in the 1 to 6 valences derived from a thiol-containing compound with 2 or more functions.

[0022] Chain contains structural units represented by the following general formula (AE-1) and structural units represented by the following general formula (AE-2).

[0023]

[0024] In general formula (AE-1), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or an alkyl group with 1 to 6 substituted or unsubstituted carbon atoms, and X represents an oxygen atom or an alkylene group with 1 to 4 substituted or unsubstituted carbon atoms. The alkyl group of Q is bonded to any carbon atom of the alkylene group of X to form a ring or not. In general formula (AE-2), R... A A group containing one or more (meth)acryloyl groups.

[0025] n is an integer from 1 to 6, and Y has a structure other than Chain, whether it is bonded or not.

[0026] According to the present invention, a polymer can be provided, wherein the polymer is obtained by the following process.

[0027] A raw material polymer is prepared by polymerizing a monomer composition containing a monomer represented by the following general formula (NBm) and maleic anhydride in the presence of a difunctional or higher thiol-containing compound; the obtained raw material polymer is reacted with a polyfunctional (meth)acrylic acid monomer and / or a monofunctional (meth)acrylic acid monomer in the presence of an alkaline catalyst to prepare a polymer precursor; and then, the obtained polymer precursor is reacted with an epoxy-containing (meth)acrylic acid compound in the presence of a catalyst to obtain a polymer.

[0028]

[0029] In the general formula (NBm), R 1 R 2 R 3 and R 4 Each is an organic group consisting of 1 to 30 hydrogen or carbon atoms, with a1 being 0, 1, or 2.

[0030] According to the present invention, it is possible to provide a polymer solution containing said polymer.

[0031] According to the present invention, a photosensitive resin composition can be provided, comprising: the aforementioned polymer solution, a polyfunctional (meth)acrylate monomer, and a photopolymerization initiator.

[0032] According to the present invention, a cured product of the aforementioned photosensitive resin composition can be provided.

[0033] The effects of the invention

[0034] The polymer of the present invention provides a resin-cured product with good sensitivity, reduced yellowing, excellent transparency, and thus excellent adhesion to substrates, etc. In other words, the polymer of the present invention provides a resin-cured product with an excellent balance of these properties. Attached Figure Description

[0035] Figure 1 This is a schematic diagram (cross-sectional view) illustrating a structural example of a liquid crystal display device and / or a solid-state imaging element.

[0036] Figure 2 It is the polymer P1 obtained in Example 1. 1 H-NMR spectrum.

[0037] Figure 3 yes Figure 2 of 1 A magnified view of the peak near 6.0 ppm in the H-NMR spectrum. Detailed Implementation

[0038] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. Furthermore, in all the drawings, the same reference numerals are used to label the same constituent elements, and descriptions are omitted where appropriate. Moreover, all the drawings are for illustrative purposes only. The shapes or size ratios of the components in the drawings do not necessarily correspond to actual objects. In this specification, the designation "a to b" in the description of numerical ranges means a or more and b or less unless otherwise specified. For example, "5 to 90%" means "5% or more and 90% or less".

[0039] In the designation of groups (atomic groups) in this specification, the designation without indicating whether they are substituted or unsubstituted includes both unsubstituted and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0040] The designation "(meth)acrylic acid" in this specification indicates that it includes both acrylic acid and methacrylic acid. The same applies to designations such as "(meth)acrylate".

[0041] In particular, "(meth)acryloyl" in this specification refers to the concept of including an acrylamide group represented by -C(=O)-CH=CH2 and a methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0042] [Polymer(A)]

[0043] The polymer (A) of this embodiment has a structure in which at least one polymer chain, represented by the following Chain, is bonded to an organic group having 1 or more and 30 or less carbon atoms in the 1 to 6 valences derived from a thiol-containing compound with 2 or more functions.

[0044] The polymer (A) can be specifically represented by the following general formula (P).

[0045]

[0046] In general formula (P), Chain contains structural units represented by general formula (AE-1) and general formula (AE-2). Polymer P containing these structural units provides a resin-cured product with good sensitivity, excellent alkali solubility, reduced yellowing, excellent transparency, and excellent adhesion to substrates, etc. In other words, the polymer of the present invention achieves an excellent balance of these properties.

[0047]

[0048] In general formula (AE-1), Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom or an alkyl group with 1 to 6 substituted or unsubstituted carbon atoms, and X represents an oxygen atom or an alkylene group with 1 to 4 substituted or unsubstituted carbon atoms. The alkyl group of Q is bonded to any carbon atom of the alkylene group of X to form a ring or is not bonded.

[0049] In general formula (AE-2), R A It is a group containing one or more (meth)acryloyl groups.

[0050] n is an integer from 1 to 6.

[0051] By means of the polymer (A) of this embodiment having the structure represented by general formula (P), it is possible to provide a resin cured product with good sensitivity, reduced yellowing and excellent transparency, and thus excellent adhesion to substrates and the like.

[0052] In general formula (AE-1), Z is not particularly limited as long as it contains one or more (meth)acryloyl groups, more preferably a group containing one to four (meth)acryloyl groups, and even more preferably a group containing one to three (meth)acryloyl groups. By optimizing the number of (meth)acryloyl groups in Z, excellent sensitivity and excellent alkali solubility (developability) are achieved; in other words, an excellent balance is achieved.

[0053] From the viewpoint of these properties, Z is preferably a group containing one (meth)acryloyl group, more preferably a group represented by the following general formula (1a).

[0054]

[0055] In general formula (1a), R is a hydrogen atom or a methyl or ethyl atom.

[0056] In the general formula (AE-1), Q is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, either substituted or unsubstituted.

[0057] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl. Examples of substituents for substituted alkyl groups having 1 to 6 carbon atoms include halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, and mercapto groups.

[0058] In the general formula (AE-1), X is an oxygen atom or an alkylene group with 1 to 4 carbon atoms, substituted or unsubstituted.

[0059] Examples of alkylene groups include methylene, ethylene, propylene, and butylene. Examples of substituents for alkylene groups with 1 to 4 carbon atoms include halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, and mercapto groups.

[0060] In general formula (AE-1), any carbon atom of the alkyl group of Q and the alkylene group of X can be bonded to form a ring. Examples of ring structures include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, decahydronaphthalene rings, benzene rings, and naphthalene rings.

[0061] In general formula (AE-2), R A The group containing one or more (meth)acryloyl groups is not particularly limited, but groups containing 1 to 6 (meth)acryloyl groups are preferred, more preferably groups containing 1 to 5 (meth)acryloyl groups, and even more preferably groups containing 2 to 5 (meth)acryloyl groups. By making R A It contains an optimal amount of (meth)acryloyl groups, which further enhances sensitivity. Furthermore, it easily achieves a higher balance between sensitivity and developability. Additionally, it facilitates further improvement in heat resistance.

[0062] The proportion of structural units represented by general formula (AE-1) in the chain of polymer (A) of this embodiment is preferably 0.5 to 20 mol%, more preferably 1 to 15 mol%. The proportion of structural units represented by general formula (AE-2) is preferably 6 to 40 mol%, more preferably 12 to 30 mol%.

[0063] As structural units represented by general formula (AE-2), examples include structural units represented by general formula (AE-2a) and general formula (AE-2b).

[0064]

[0065] In general formula (AE-2a), R S It is a group containing only one (meth)acryloyl group. In particular, in the design of conventional photosensitive resin compositions, when the curability is increased to improve sensitivity, over-curing tends to occur and the developability tends to deteriorate. On the other hand, when the developability is improved, curing tends to become insufficient. Therefore, the chain of polymer (A) preferably contains structural units represented by the general formula (AE-2a), thereby achieving a good balance between sensitivity and developability.

[0066] R S For example, groups represented by the following general formula (Sa).

[0067]

[0068] In the general formula (Sa), X 10 It is a divalent organic group, where R is a hydrogen atom or a methyl group.

[0069] X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.

[0070] In the general formula (Sa), X 10 It is a divalent organic group, where R is a hydrogen atom or a methyl group.

[0071] X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.

[0072] As X 10 The divalent organic group, preferably an alkylene group, may contain a portion of an ether group (-O-). The alkylene group may be linear or branched, but linear is more preferred.

[0073] As X 10 The divalent organogroup is more preferably a straight-chain alkylene group with a total carbon number of 3 to 6. By appropriately selecting X... 10 The number of carbon atoms (X) 10 With the chain length), the structural unit represented by the general formula (AE-2a) is more likely to participate in the cross-linking reaction, which can improve the sensitivity.

[0074] X 10 The divalent organogroup (e.g., alkylene) can be replaced by any substituent. Examples of substituents include alkyl, aryl, alkoxy, and aryloxy groups.

[0075] Moreover, X 10 The divalent organic group can also be any group other than alkylene. For example, it can be a divalent group formed by linking one or more groups selected from alkylene, cycloalkylene, arylene, ether, carbonyl, carboxyl, etc.

[0076] The proportion of structural units represented by general formula (AE-2a) in the chain of polymer (A) of this embodiment is preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

[0077] In general formula (AE-2b), R D The group containing two or more (meth)acryloyl groups is not particularly limited, but groups containing 2 to 6 (meth)acryloyl groups are more preferred, and groups containing 3 to 5 (meth)acryloyl groups are even more preferred. By making R DIt contains an optimal amount of (meth)acryloyl groups, which further enhances sensitivity. Furthermore, it easily achieves a higher balance between sensitivity and developability. Additionally, it facilitates further improvement in heat resistance.

[0078] Furthermore, from the perspective of further improving sensitivity, in terms of spatial steric hindrance, R D Preferably, it contains two or more acryloyl groups (represented by -C(=O)-CH=CH2).

[0079] R D Preferably, the group is represented by the following general formula (1b), (1c) or (1d). By having such a group, it is easier to obtain the various effects mentioned above.

[0080]

[0081] In general formula (1b).

[0082] k is 2 or 3.

[0083] R can be a hydrogen atom or a methyl group, and multiple Rs can be the same or different.

[0084] X 1 A single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z being -O- or -OCO-, X being an alkylene group having 1 to 6 carbon atoms), with multiple X groups present. 1 Same or different.

[0085] X 1 ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-).

[0086] X 2 It is an organic group with a carbon number of 1 to 12 and a valence of k+1.

[0087] In terms of further improving sensitivity (ease of polymerization), R is preferably a hydrogen atom.

[0088] k can be 2 or 3, but from the viewpoint of further improving the availability or sensitivity of raw materials, 3 is preferred.

[0089] When X 1 When the alkylene group has 1 to 6 carbon atoms, the alkylene group can be either straight-chain or branched.

[0090] When X 1 When X is an alkylene group having 1 to 6 carbon atoms, 1 Preferably, it is a straight-chain alkylene group, more preferably a straight-chain alkylene group having 1 to 3 carbon atoms, and even more preferably -CH2-(methylene).

[0091] When X 1 When the group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group with 1 to 6 carbon atoms) has 1 to 6 carbon atoms, the alkylene group of X can be either straight-chain or branched.

[0092] The alkylene group of X having 1 to 6 carbon atoms is preferably a straight-chain alkylene group, more preferably a straight-chain alkylene group having 1 to 3 carbon atoms, and even more preferably -CH2-CH2-(ethylene) or -CH2-CH(CH3)-.

[0093] When X 1 When it is an alkylene group having 1 to 6 carbon atoms, its specific manner is the same as X. 1 same.

[0094] When X 1 When ' is a group represented by -X'-Z'-, the specific form of X' is the same as that of X above.

[0095] As X 2 The organic group with a carbon number of 1 to 12 and a valence of k+1 can be any group formed by removing k+1 hydrogen atoms from any organic compound. "Any organic compound" here 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.

[0096] X 2 For example, the group is formed by removing k+1 hydrogen atoms from a straight-chain or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, the group is formed by removing k+1 hydrogen atoms from a straight-chain hydrocarbon having 1 to 3 carbon atoms. In addition, the hydrocarbon here may contain oxygen atoms (e.g., ether bonds or hydroxyl groups). Moreover, the hydrocarbon is preferably a saturated hydrocarbon.

[0097] As another way, X 2 It can be a group containing a cyclic structure. Examples of groups containing a cyclic structure include groups containing alicyclic structures and groups containing heterocyclic structures (e.g., isocyanuric acid structures).

[0098]

[0099] In general formula (1c).

[0100] k, R, X 1 and X 2 respectively with R, k, and X in the above general formula (1b) 1 and X 2 The same meaning, multiple Rs are the same or different from each other, multiple Xs 1 They are the same or different from each other.

[0101] X 3 It is a divalent organic group with 1 to 6 carbon atoms.

[0102] X 4 and X 5 They are either single bonds or divalent organic groups with 1 to 6 carbon atoms, and can be independent of each other.

[0103] X 6 It is a divalent organic group with 1 to 6 carbon atoms.

[0104] Regarding R, k, X 1 and X 2 The specific methods and preferred methods are the same as those described in general formula (1b).

[0105] As X 3 and X 6 The hydrocarbon is a divalent organic group having 1 to 6 carbon atoms. Examples of such groups include those formed by removing two hydrogen atoms from a straight-chain or branched hydrocarbon having 1 to 6 carbon atoms. Furthermore, the hydrocarbon may contain oxygen atoms (e.g., an ether bond or a hydroxyl group). Moreover, the hydrocarbon is preferably a saturated hydrocarbon.

[0106] As X 4 and X 5 The organogroup having 1 to 6 carbon atoms is a divalent organic group, and examples include straight-chain or branched alkylene groups. The straight-chain or branched alkylene groups preferably have 1 to 3 carbon atoms.

[0107]

[0108] In the general formula (1d), n is an integer from 2 to 5, preferably 2 or 3.

[0109] The proportion of structural units represented by general formula (AE-2b) in the chain of polymer (A) of this embodiment is preferably 1 to 30 mol%, more preferably 2 to 20 mol%.

[0110] The chain of the polymer (A) in this embodiment can contain structural units represented by the following general formula (AE), which are composed of structural units represented by general formula (AE-1) and structural units represented by general formula (AE-2).

[0111]

[0112] In the general formula (AE), Z, Q, and X have the same meaning as in the general formula (AE-1), and R... A It has the same meaning as the general formula (AE-2).

[0113] The proportion of structural units represented by general formula (AE) in the chain of polymer (A) of this embodiment is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%.

[0114] The chain of polymer (A) in this embodiment can contain structural units represented by the following general formula (DE), which are composed of structural units represented by general formula (AE-1) and structural units represented by general formula (AE-2b). Polymer (A) containing structural units represented by the following general formula (DE) in the chain can provide a resin cured product with good sensitivity, excellent alkali solubility, further reduced yellowing, excellent transparency, and excellent adhesion to substrates, etc. In other words, the polymer of the present invention achieves a better balance of these properties, with particularly excellent sensitivity.

[0115]

[0116] In the general formula (DE), Q, X, and Z have the same meaning as in the general formula (AE-1), and R D It has the same meaning as the general formula (AE-2b).

[0117] The proportion of structural units represented by general formula (DE) in all structural units contained in the chain of polymer (A) of this embodiment is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%.

[0118] The chain of the polymer (A) in this embodiment can contain structural units composed of structural units represented by general formula (AE-1) and structural units represented by general formula (AE-2a), that is, structural units represented by the following general formula (SE).

[0119]

[0120] In the general formula (SE), Z, Q, and X have the same meaning as in the general formula (AE-1), and R... S It has the same meaning as the general formula (AE-2a).

[0121] When polymer (A) contains structural units represented by general formula (SE), the proportion of structural units represented by general formula (SE) in all structural units contained in the chain of polymer (A) is preferably 3 to 35 mol%, more preferably 7 to 25 mol.

[0122] The chain of the polymer (A) in this embodiment may also contain structural units represented by the following general formula (NB).

[0123]

[0124] In the general formula (NB), R 1 R 2 R 3 and R 4 Each is an organic group consisting of 1 to 30 hydrogen or carbon atoms, where a1 is 0, 1, or 2.

[0125] The structural unit represented by the general formula (NB) is chemically robust. Therefore, the polymer (A) containing it as a structural unit exhibits minimal weight loss and stability upon heat treatment. Consequently, photosensitive resin compositions containing polymer (A) are suitable for manufacturing films or color filters used in liquid crystal display devices or solid-state imaging elements requiring heat resistance.

[0126] As can constitute R 1 ~R 4 Organic groups with 1 to 30 carbon atoms include substituted or unsubstituted straight-chain or branched alkyl groups with 1 to 30 carbon atoms. More specifically, examples include alkyl, alkenyl, alkynyl, alkylene, aryl, aralkyl, alkanearyl, cycloalkyl, alkoxy, heterocyclic, and carboxyl groups.

[0127] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl.

[0128] Examples of alkenyl groups include allyl, pentenyl, and vinyl.

[0129] Examples of alkynyl groups include the ethynyl group.

[0130] Examples of alkylene derivatives include methylene and ethylidene.

[0131] Examples of aryl groups include tolyl, xylyl, phenyl, naphthyl, and anthracene group.

[0132] Examples of aralkyl groups include benzyl and phenethyl.

[0133] Examples of alkylaryl groups include tolyl and xylyl.

[0134] Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0135] Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, neopentoxy, and n-hexoxy.

[0136] Examples of heterocyclic groups include epoxy groups and oxetanyl groups.

[0137] R is the structural unit represented by the general formula (NB). 1 R 2 R 3 and R 4 Preferably, it is hydrogen or alkyl, more preferably hydrogen.

[0138] Additionally, R 1 R 2 R 3 and R 4 The hydrogen atoms in organic groups with 1 to 30 carbon atoms can be replaced by any atomic group. For example, they can be replaced by fluorine atoms, hydroxyl groups, carboxyl groups, etc. More specifically, as R 1 R 2 R 3 and R 4 Organic groups with 1 to 30 carbon atoms can be selected, such as fluorinated alkyl groups.

[0139] In the structural unit represented by the general formula (NB), a1 is preferably 0 or 1, and more preferably 0.

[0140] The proportion of structural units represented by general formula (NB) in all structural units contained in the chain of polymer (A) is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%.

[0141] From the viewpoint of the effects of the present invention, the chain of the polymer (A) of this embodiment may further contain structural units represented by the following general formula (D) and / or structural units represented by the following general formula (S).

[0142]

[0143] In general formula (D), R D It has the same meaning as the general formula (AE-2b).

[0144] When the chain of polymer (A) contains structural units represented by general formula (D), the proportion of structural units represented by general formula (D) in all structural units contained in the chain of polymer (A) is preferably 0.5 to 25 mol%, more preferably 1 to 18 mol%.

[0145]

[0146] In the general formula (S), R S It has the same meaning as the general formula (AE-2a).

[0147] When the chain of polymer (A) contains structural units represented by general formula (S), the proportion of structural units represented by general formula (S) among all structural units contained in the chain of polymer (A) is preferably 3 to 35 mol%, more preferably 5 to 25 mol%.

[0148] In this embodiment, in addition to the structural units described above, polymer (A) may also contain structural units represented by general formula (MA). The structural unit represented by general formula (MA) generates two carboxyl groups as shown in general formula (M) below by ring-opening with an alkaline developer. Therefore, polymer (A) containing this structural unit exhibits excellent developability. When the chain of polymer (A) contains structural units represented by general formula (MA), the structural units represented by general formula (MA) among all structural units contained in the chain of polymer (A) are preferably 1 to 30 mol%, more preferably 2 to 25 mol%.

[0149]

[0150] Furthermore, the content (ratio) of each structural unit contained in the chain of polymer (A) can be determined based on the amount (molar amount) of raw materials used in the synthesis of the chain of polymer (A), the amount of raw materials remaining after synthesis, and various spectra (e.g., IR spectra, etc.). 1 H-NMR spectroscopy, 13 The presence and peak area of ​​the peaks in the C-NMR spectrum are used to deduce / calculate the result.

[0151] From the viewpoint of the effects of the present invention, the chain of the polymer (A) of this embodiment may further contain structural units represented by the following general formula (E) and / or structural units represented by the following general formula (EE).

[0152]

[0153] In general formulas (E) and (EE), Z, Q, and X have the same meaning as in general formula (AE-1). In general formula (EE), there may be multiple instances of Z, Q, and X that are the same or different.

[0154] When polymer (A) contains structural units represented by general formula (E), the proportion of structural units represented by general formula (E) in all structural units contained in the chain of polymer (A) is preferably 1 to 12 mol%, more preferably 2 to 9 mol%.

[0155] When polymer (A) contains structural units represented by general formula (EE), the proportion of structural units represented by general formula (EE) in all structural units contained in the chain of polymer (A) is preferably 1 to 10 mol%, more preferably 2 to 8 mol%.

[0156] In order to adjust the solubility of polymer (A) in solvents, etc., the chain of polymer (A) in this embodiment may also contain structural units represented by the following general formula (M).

[0157]

[0158] When polymer (A) contains structural units represented by general formula (M), the proportion of structural units represented by general formula (M) in all structural units contained in the chain of polymer (A) is preferably 1 to 15 mol%, more preferably 2 to 10 mol%.

[0159] The chain of the polymer represented by the general formula (P) in this embodiment may contain divalent structural units derived from copolymeric compounds having double bonds.

[0160] The structural unit may contain at least one structural unit derived from compounds such as: substituted or unsubstituted indene, maleimide, styrene, acenaphthylene, norbornadiene, dihydrofuran, terpene compounds (e.g., pinene, limonene, etc.), linear alkenes (e.g., pentene, etc.), cyclic alkenes (e.g., cyclohexene), cyclododecanetriene, tricycloundecane, dialkyl fumarate (e.g., dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth)acrylic acid compounds (e.g., methyl methacrylate, methyl acrylate), vinyl acetate, vinyl ethers (e.g., 2-hydroxyethyl vinyl ether, etc.).

[0161] Examples of substituents that can be present in these monomers include alkyl and aryl groups. More specifically, examples of substituted indenes include methyl indene. Examples of substituted maleimides include cyclohexylmaleimide and phenylmaleimide. Examples of substituted styrene include methylstyrene and vinyltoluene.

[0162] The Chain preferably contains a structural unit represented by general formula (1) (a divalent structural unit derived from substituted or unsubstituted indene), a structural unit represented by general formula (2) (a divalent structural unit derived from substituted or unsubstituted maleimide), a structural unit represented by general formula (3) (a divalent structural unit derived from substituted or unsubstituted styrene), or a structural unit represented by general formula (4) (a divalent structural unit derived from substituted or unsubstituted norbornene).

[0163]

[0164] In general formula (1), R 1 and R2 Each of the following groups independently represents a hydrogen atom, an alkyl group, or an aryl group. In general formula (2), R... 3 Represents a hydrogen atom, alkyl group, or aryl group. In general formula (3), R 4 ~R 6 Each of the following groups independently represents a hydrogen atom, an alkyl group, or an aryl group. In general formula (4), R... 7 ~R 10 Each can be an organic group that independently represents a hydrogen atom, a hydroxyl group, or an organic group with 1 to 30 carbon atoms.

[0165] In general formula (P), Y is an organogroup (i) with 1 to 30 carbon atoms in the 1 to 6 valences derived from a thiol-containing compound with 2 or more functions.

[0166] In this embodiment, the number of functional groups is the number of thiol groups. That is, the thiol-containing compound contains two or more thiol groups, and the organic group (i) is bonded to the chain via one to six thioether groups derived from the thiol group. The organic group (i) may have thiol groups that do not participate in the bonding with the chain, and the polymer (A) can be obtained as a mixture of resins in which the number of n (number of bonds) is 1 to 6.

[0167] The organic group (i) having 1 or more and 30 or fewer carbon atoms is 2-functional or more, preferably 3-functional or more. The upper limit is not particularly limited, but is 6-functional or less.

[0168] From the viewpoint of the effects of the present invention, the valence of the organic group (i) having 1 or more and 30 or less carbon atoms is 1 to 6, preferably 2 to 6, and more preferably 3 to 6.

[0169] The organogroup (i) having 1 or more but less than 30 carbon atoms in the 1 to 6 valence range may contain one or more atoms selected from O, N, S, P, and Si. Examples of organogroups (i) having 1 or more but less than 30 carbon atoms in the 1 to 6 valence range include alkyl, alkenyl, alkynyl, alkylene, aryl, aralkyl, alkylaryl, cycloalkyl, alkoxy, and heterocyclic groups having 1 to 6 thioether groups (-S-* (* is a linking bond)).

[0170] 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. Examples of alkenyl groups include allyl, pentenyl, and vinyl.

[0171] As an alkynyl group, the acetylenic group can be cited as an example.

[0172] Examples of alkylene groups include methylene and ethylene. Examples of aryl groups include tolyl, xylyl, phenyl, naphthyl, and anthracene.

[0173] Examples of aryl alkyl groups include benzyl and phenethyl.

[0174] Examples of alkylaryl groups include tolyl and xylyl.

[0175] Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0176] Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, neopentoxy, and n-hexyloxy.

[0177] Examples of heterocyclic groups include epoxy and oxo-heterocyclic butyl groups.

[0178] Examples of thiol-containing compounds with two or more functions include compounds represented by the following chemical formulas (s-1) to (s-21).

[0179]

[0180]

[0181]

[0182] In this embodiment, from the viewpoint of the effects of the present invention, the thiol-containing compound with two or more functions preferably contains a thiol-containing compound with three or more functions. Furthermore, the thiol-containing compound preferably contains an ester structure.

[0183] In this embodiment, among the compounds represented by chemical formulas (s-1) to (s-21), the thiol-containing compounds with two or more functions more preferably contain compounds represented by chemical formulas (s-1) to (s-3), (s-5) and (s-8) to (s-10), and even more preferably contain compounds represented by chemical formulas (s-1) to (s-3), (s-5) and (s-9).

[0184] A thiol-containing compound with two or more functions can be used alone or in combination.

[0185] The organogroup (i) having 1 to 30 carbon atoms with a valence of 1 to 6 has a thioether group (-S-* (* being a linking bond)) at its terminal, derived from the thiol group of these thiol-containing compounds, and is bonded to the structural units contained in the chain via the thioether group. The organogroup (i) may have a thiol group that does not participate in the bonding with the chain.

[0186] In general formula (P), Y may be bonded or unbonded with a structure other than Chain. Specifically, general formula (P) can be represented by the following general formula (P').

[0187]

[0188] In the general formula (P'), Chain and Y have the same meaning as in general formula (P). p is an integer greater than or equal to 1, q is an integer greater than or equal to 0, and p+q is from 1 to 6.

[0189] The Q structure, other than Chain, is not particularly limited as long as it can be bonded to Y. Various components used in the synthetic reaction can be listed, such as structural units selected from the structural units represented by the general formula (AE) (structural units represented by the general formula (DE) and / or the structural units represented by the general formula (SE)), structural units represented by the general formula (D), structural units represented by the general formula (S), structural units represented by the general formula (NB), structural units represented by the general formula (MA), and at least one divalent structural unit derived from a copolymeric compound having a double bond, or a group derived from the thiol-containing compound with more than two functions.

[0190] The polymer (A) of this embodiment preferably has the structure represented by the following general formula (P1). Structural unit A and structural unit B in general formula (P1) typically constitute the main chain of polymer (A).

[0191]

[0192] In the general formula (P1), p, q and r represent the molar contents of A, B and C in the polymer, respectively, and p+q+r=1.

[0193] p is greater than 0, preferably 0.25 to 0.75.

[0194] q is greater than 0, preferably 0.25 to 0.75.

[0195] r is 0 or more, preferably 0 to 0.5, more preferably 0 to 0.3, and particularly preferably 0 to 0.1.

[0196] p, q, or r are the same or different in each of the n structural units within [].

[0197] n is an integer from 1 to 6.

[0198] X is a hydrogen group or an organogroup with 1 or more but less than 30 carbon atoms. This organogroup with 1 or more but less than 30 carbon atoms combines with R to form the general formula (NB). 1 ~R 4 Organic groups with 1 or more carbon atoms and less than 30 are the same.

[0199] Y is an organogroup (i) derived from a thiol-containing compound with 1 to 30 carbon atoms in the 1 to 6 valences, wherein the thioether group derived from the thiol group is bonded to the structural unit within []n.

[0200] A contains the structural unit represented by the general formula (NB).

[0201] B contains the structural unit represented by the general formula (AE). In this embodiment, it may contain at least one structural unit selected from the structural units represented by the general formula (DE) and the general formula (SE).

[0202] B may also include, as needed, at least one structural unit selected from the structural units represented by the general formula (D), the general formula (S), the general formula (MA), the general formula (E), the general formula (EE), and the general formula (M).

[0203] C contains structural units derived from the copolymeric compound having double bonds.

[0204] There exist multiple A's, B's, or C's that are the same or different from each other.

[0205] In addition, in general formula (P1), the order of the bonds A, B and C is not particularly restricted, and any one of A, B and C can be bonded to Y.

[0206] In general formula (P1), Y is bonded to or unbonded to other structures besides the polymer chain represented by []n. Specifically, general formula (P1) can be represented by the following general formula (P1').

[0207]

[0208] In the general formula (P1'), A, B, C, X, Y, p, q, and r have the same meaning as in general formula (P1). Q has the same meaning as in general formula (P'). a is an integer greater than or equal to 1, b is an integer greater than or equal to 0, and a+b is from 1 to 6.

[0209] When the compound represented by the chemical formula (s-2) is used as the thiol-containing compound with more than two functions, the polymer (A) of this embodiment can, for example, have a structure represented by the following general formula (I).

[0210]

[0211] In general formula (I), A, B, C, X, p, q, and r have the same meaning as in general formula (P1). The A, B, C, X, p, q, and r contained in the four structural units within [] may be the same or different.

[0212] In general formula (I), the bonding order of A, B, and C is not particularly limited, and any one of A, B, and C may be bonded to a thioether group. Furthermore, general formula (I) is exemplified by "a thioether group derived from the four mercapto groups of the compound represented by chemical formula (S-2) bonded to four structural units within []. However, it may also be a structure with one to three structural units within []. In this embodiment, polymer (A) can be obtained as a mixture containing at least one compound with one to four structures within [].

[0213] The weight-average molecular weight (Mw) of polymer (A) is, for example, 1,000 to 20,000, preferably 1,500 to 17,500, more preferably 2,000 to 15,000, and even more preferably 3,000 to 10,000. By appropriately adjusting the weight-average molecular weight, the sensitivity or solubility in alkaline developing solutions can be adjusted.

[0214] Furthermore, the dispersion (weight-average molecular weight Mw / number-average molecular weight Mn) of polymer (A) is preferably 1.0 to 6.0, more preferably 1.0 to 5.5, and even more preferably 1.0 to 5.0. By appropriately adjusting the dispersion, the physical properties of polymer (A) can be made homogeneous, which is therefore preferred. In addition, these values ​​can be determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0215] The glass transition temperature of polymer (A) is preferably 150–250°C, more preferably 170–230°C. Polymer (A) has a relatively high glass transition temperature due to its predominantly containing structural units represented by the general formula (NB). This is preferable from the viewpoint of ensuring the stable existence of patterns formed on the substrate during the manufacture of liquid crystal display devices or solid-state imaging elements. Furthermore, the glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0216] The content (ratio) of each structural unit contained in the polymer (A) of this embodiment can be determined based on the amount of raw materials input (molar amount) during polymer synthesis, the amount of raw materials remaining after synthesis, and the peak areas of various spectra (e.g., 1 The peak area of ​​H-NMR is used to deduce / calculate the result.

[0217] <Method for manufacturing polymer (A)>

[0218] The method for manufacturing polymer (A) according to this embodiment will be described.

[0219] Polymer (A) can be manufactured (synthesized) by any method. For example, polymer (A) can be manufactured by the following process.

[0220] Step (I): Prepare a raw material polymer containing a structural unit represented by general formula (NB), a structural unit represented by general formula (MA), and an organic group (i) having 1 or more and 30 or less carbon atoms with 1 to 6 valences.

[0221] Step (II): The raw material polymer obtained in step (I) is reacted with a compound having hydroxyl and two or more (meth)acryloyl groups (hereinafter referred to as "polyfunctional (meth)acrylic acid monomers") and / or a compound having hydroxyl and one (meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acrylic acid monomers") in the presence of an alkaline catalyst to prepare a polymer precursor containing the structural unit represented by general formula (NB), an organogroup (i) having 1 or more and 30 or less carbon atoms in the 1 to 6 valences, a structural unit represented by general formula (D), and / or a structural unit represented by general formula (S) and, where appropriate, a structural unit represented by general formula (MA).

[0222] And, step (III): reacting the polymer precursor obtained in step (II) with an epoxy-containing (meth)acrylic acid compound in the presence of a catalyst to prepare a polymer (A) containing a structural unit represented by general formula (NB), an organogroup (i) having 1 or more and 30 or less carbon atoms in the 1 to 6 valences, a structural unit represented by general formula (D) and / or a structural unit represented by general formula (S), a structural unit represented by general formula (AE) (a structural unit represented by general formula (DE) and / or a structural unit represented by general formula (SE)) and, where appropriate, a structural unit represented by general formula (MA).

[0223] When both polyfunctional (meth)acrylic acid monomers and monofunctional (meth)acrylic acid monomers are used in step (II), it is preferable to first react the polyfunctional (meth)acrylic acid monomer with the raw material polymer, and then react the monofunctional (meth)acrylic acid monomer with the obtained reaction mixture.

[0224] (Process (I))

[0225] The step (I) of preparing a raw material polymer containing a structural unit represented by general formula (NB), a structural unit represented by general formula (MA), and an organic group (i) having 1 to 30 carbon atoms with 1 to 6 valences can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by general formula (NBm) and maleic anhydride in the presence of a thiol-containing compound with 2 or more functions. Furthermore, the R of general formula (NBm) 1 R 2 R 3 and R 4 The definition of a1 is the same as that of the general formula (NB). The preferred method is also the same.

[0226]

[0227] Examples of monomers represented by the general formula (NBm) include norbornene, bicyclo[2.2.1]-hept-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-phenylethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, and 5-norbornene-2,3-dicarboxylic anhydride. During polymerization, the monomer represented by the general formula (NBm) can be a single monomer or a combination of two or more monomers.

[0228] In addition to the monomers mentioned above, the monomer composition may also contain other monomers.

[0229] As other monomers, any known compound capable of polymerization with a double bond can be used without particular limitation, provided it is a copolymerizable compound. Examples of other monomers include substituted or unsubstituted compounds such as indene, maleimide, styrene, acenaphthene, norbornene, dihydrofuran, terpenes (e.g., pinene, limonene, etc.), linear olefins (e.g., pentene, etc.), cyclic olefins (e.g., cyclohexene), cyclododecanetriene, tricycloundecane, dialkyl fumarate (e.g., dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth)acrylic acid compounds (e.g., methyl methacrylate, methyl acrylate), vinyl acetate, and vinyl ethers (e.g., 2-hydroxyethyl vinyl ether, etc.). In step (I), the monomer represented by the general formula (NBm), maleic anhydride, and other monomers as needed can be polymerized (addition polymerization) in the presence of the thiol-containing compound with more than two functions.

[0230] Examples of thiol-containing compounds with two or more functional groups include those represented by the chemical formulas (s-1) to (s-21), but are not limited to these. A single thiol-containing compound with two or more functional groups may be used, or two or more may be used in combination.

[0231] The polymerization method is not limited, but free radical polymerization using a free radical polymerization initiator is preferred. Examples of polymerization initiators include azo compounds and organic peroxides.

[0232] Examples of azo compounds include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionic acid) ester, and 1,1'-azobis(cyclohexaneformitrile) (ABCN).

[0233] Examples of organic peroxides include hydrogen peroxide, di(tert-butyl)peroxide (DTBP), benzoyl peroxide (BPO), and methyl ethyl ketone peroxide (MEKP).

[0234] Regarding polymerization initiators, only one type can be used, or two or more types can be used in combination.

[0235] Organic solvents such as diethyl ether, tetrahydrofuran, toluene, and methyl ethyl ketone can be used as solvents in polymerization reactions. The polymerization solvent can be a single solvent or a mixture of solvents.

[0236] The synthesis of the raw material polymer can be carried out by the following steps: dissolving the monomer represented by the general formula (NBm), maleic anhydride, and polymerization initiator in a solvent and adding them to a reaction vessel, followed by heating, and adding the thiol-containing compound with more than two functions dropwise while carrying out addition polymerization. The heating temperature is, for example, 50–80°C, and the heating time is, for example, 5–20 hours.

[0237] The molar ratio of the monomer represented by the general formula (NBm) to maleic anhydride when added to the reaction vessel is preferably 0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1:1.

[0238] Through this process, "raw material polymers" can be obtained.

[0239] Furthermore, the raw material polymer can be any of the following: random copolymer, alternating copolymer, block copolymer, periodic copolymer, etc. Typically, it is a random copolymer or an alternating copolymer. Additionally, maleic anhydride is generally known to be a monomer with strong alternating copolymerization properties.

[0240] In addition, after synthesizing the raw material polymer, a process can be performed to remove low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators.

[0241] Specifically, the organic phase containing the synthesized raw polymer and low molecular weight components is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol to precipitate the monomers. The precipitate is filtered and dried, thereby improving the purity of the raw polymer.

[0242] (Process (II))

[0243] By reacting the raw material polymer obtained in step (I) with a polyfunctional (meth)acrylic acid monomer and / or a monofunctional (meth)acrylic acid monomer in the presence of an alkaline catalyst, a portion of the structural unit represented by the general formula (MA) contained in the raw material polymer undergoes ring opening to form a structural unit represented by the general formula (D) and / or a structural unit represented by the general formula (S), thereby obtaining a polymer precursor containing the structural unit represented by the general formula (NB), the organic group (i) having 1 or more and 30 or less carbon atoms in the 1 to 6 valences, and the structural unit represented by the general formula (D) and / or the structural unit represented by the general formula (S), and depending on the case, a structural unit represented by the general formula (MA).

[0244] More specifically, the first step is to prepare a solution by dissolving the raw polymer in a suitable organic solvent. As organic solvents, individual 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 not limited to these; various organic solvents used in the synthesis of organic compounds or polymers can be used.

[0245] When a polymer containing both the structural units represented by general formula (NB), general formula (D), and general formula (S) is obtained, a polyfunctional (meth)acrylic acid monomer is then added to the above solution. A basic catalyst is further added. The solution is then appropriately mixed to prepare a homogeneous solution, thereby obtaining a polymer containing a structure in which "at least structural units of general formula (NB) and structural units of general formula (D) are bonded to the organic group (i) having 1 to 30 carbon atoms via 1 to 6 thioether groups" (step (II-i)).

[0246] Examples of polyfunctional (meth)acrylic acid monomers that can be used herein include compounds represented by general formula (1b-m), compounds represented by general formula (1c-m), and compounds represented by general formula (1d-m). In general formula (1b-m), k, R, and X... 1 X 1 'and X 2 The definition and specific method are the same as those in the general formula (1b) above. Furthermore, k, R, and X in general formula (1c-m) are... 1 X 2 X 3 X 4 X 5 and X 6 The definition and specific method are the same as in the general formula (1c) above. The n in the general formula (1c-m) is the same as in the general formula (1d) above.

[0247]

[0248]

[0249] The following are examples of polyfunctional (meth)acrylic acid compounds having hydroxyl groups that can be preferably used. Alternatively, compounds in which some or all of the acryloyl groups of the compounds shown below are (meth)acryloyl groups (or vice versa) can also be used.

[0250]

[0251]

[0252] Next, the monofunctional (meth)acrylic acid monomer is reacted with the polymer obtained in step (II-i) in the presence of an alkaline catalyst, thereby obtaining a polymer precursor (step (II-ii)) containing a structure of "at least a structural unit of general formula (NB), a structural unit of general formula (D) and a structural unit of general formula (S) and the organic group (i) having 1 to 30 carbon atoms bonded together via 1 to 6 thioether groups".

[0253] As a basic catalyst, amine compounds or nitrogen-containing heterocyclic compounds known in the field of organic synthesis can be appropriately used. For example, amine compounds or nitrogen-containing heterocyclic compounds such as triethylamine, pyridine, and dimethylaminopyridine can be used as catalysts. The amount of basic catalyst used can be set to approximately 10 to 60 parts by mass relative to 100 parts by mass of the starting polymer. However, it should be noted that excessive use of a basic catalyst may increase the amount of acid required for neutralization, making purification more complicated.

[0254] The ring-opening / AE structural units of the general formula (MA) structural units contained in the raw material polymer are formed by heating the above solution at 60-80°C for about 3-9 hours.

[0255] Alternatively, for example, by adding a monofunctional (meth)acrylic acid compound with hydroxyl groups to the reaction system during the above heating process, the structural unit represented by the general formula (SE) can be generated in the polymer (A).

[0256] From the viewpoint of steric hindrance, monofunctional (meth)acrylic acid compounds with hydroxyl groups tend to react more readily with the starting polymer than polyfunctional (meth)acrylic acid compounds with hydroxyl groups. Therefore, when generating the structural unit represented by the general formula (SE) in polymer (A), it is preferable to add the monofunctional (meth)acrylic acid compound with hydroxyl groups to the reaction system rather than introducing it from the outset.

[0257] Examples of monofunctional (meth)acrylic acid compounds with hydroxyl groups include those represented by the following general formula (Sa-m).

[0258] In the general formula (Sa-m), regarding X 10 The definition of R is the same as that in the general formula (Sa).

[0259]

[0260] Specific examples of compounds represented by the general formula (Sa-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanediethanol 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.

[0261] When a polymer containing the structural unit represented by general formula (NB), the organic group (i) having 1 or more and 30 or less carbon atoms in the 1 to 6 valences, and any one of the structural units represented by general formula (AE) and general formula (DE), after step (I), only one of steps (II-i) and (II-ii) needs to be performed.

[0262] (Process (III))

[0263] The polymer precursor obtained in step (II) is reacted with an epoxy-containing (meth)acrylic acid compound in the presence of a catalyst, and the structural unit represented by general formula (AE) (the structural unit represented by general formula (DE) and / or the structural unit represented by general formula (SE)) is formed by the reaction of the carboxyl group of the polymer precursor with the epoxy group of the epoxy-containing (meth)acrylic acid compound, thereby preparing a polymer (A) containing the structural unit represented by general formula (NB), the organic group (i) having 1 or more and 30 or less carbon atoms in the 1 to 6 valence, the structural unit represented by general formula (D) and / or the structural unit represented by general formula (S), the structural unit represented by general formula (AE) (the structural unit represented by general formula (DE) and / or the structural unit represented by general formula (SE)), and, depending on the case, the structural unit represented by general formula (MA).

[0264] Step (III) is preferably carried out by adding an epoxy-containing (meth)acrylic acid compound to a reaction system containing the polymer precursor obtained in step (II-ii).

[0265] The reaction between the polymer precursor and the epoxy-containing (meth)acrylic acid compound is carried out in the presence of a basic catalyst. The basic catalyst can be used directly from the catalyst remaining in the reaction system obtained in step (II-ii). Therefore, regarding step (III), it is preferable to carry it out by adding the epoxy-containing (meth)acrylic acid compound to the reaction mixture containing the polymer precursor obtained in step (II-ii) in situ, without isolating and purifying the polymer precursor from the reaction mixture containing the polymer precursor obtained in step (II-ii) or neutralizing the basic catalyst contained in the mixture.

[0266] Specifically, the reaction solution obtained by adding an epoxy-containing (meth)acrylic acid compound to the reaction mixture containing the polymer precursor is preferably heated at 60-80°C for about 1-9 hours, thereby generating polymer (A) by reacting the carboxyl group of the polymer precursor with the epoxy group of the epoxy-containing (meth)acrylic acid compound to form the structural unit represented by general formula (AE) (the structural unit represented by general formula (DE) and / or the structural unit represented by general formula (SE)).

[0267] Examples of epoxy-containing (meth)acrylic acid compounds include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, glycidyl acrylate, etc., and one or more of these compounds can be used.

[0268] The amount of the epoxy-containing (meth)acrylic acid compound added is preferably 0.1 to 3.0 moles relative to 1 mole of the carboxyl group of the polymer precursor.

[0269] Alternatively, it is also preferable to include a step (II') between step (II) and step (III) in which the structural unit represented by formula (MA) in the polymer precursor is treated with water in the presence of a catalyst to open the ring, thereby forming the structural unit represented by formula (M).

[0270] Specifically, it is preferable to carry out the reaction by adding water to a reaction system containing the polymer precursor P obtained in step (II). As the catalyst used, a basic catalyst can be used, and the same basic catalyst used in step (II) can be used. Specific examples of basic catalysts include amine compounds or nitrogen-containing heterocyclic compounds such as triethylamine, pyridine, and dimethylaminopyridine.

[0271] In step (II'), water is added to the reaction system containing polymer precursor P, and the resulting reaction solution is preferably heated at 60–80°C for approximately 0.25–6 hours, thereby opening the ring of the structural unit of formula (MA) contained in polymer precursor P to generate the structural unit represented by formula (M). This reaction is carried out in the presence of a basic catalyst. The basic catalyst can be directly used from the catalyst remaining in the reaction system obtained in step (II). Therefore, this step is preferably carried out by adding water in situ to the reaction mixture containing polymer precursor P obtained in step (II), without needing to isolate and purify the polymer precursor P from the reaction mixture containing the polymer precursor P obtained in step (II) or neutralize the basic catalyst contained in the mixture.

[0272] Next, the polymer precursor obtained in step (II') can be used for the reaction in step (III). In step (III), the polymer precursor obtained in step (II') is reacted with an epoxy-containing (meth)acrylic acid compound in the presence of a catalyst, and the structural unit represented by general formula (AE) (the structural unit represented by general formula (DE) and / or the structural unit represented by general formula (SE)) is formed by the reaction of the carboxyl group of the polymer precursor with the epoxy group of the epoxy-containing (meth)acrylic acid compound. Thus, a polymer (A') containing the structural unit represented by general formula (NB), the organic group (i) having 1 or more and 30 or less carbon atoms in the 1 to 6 valence, the structural unit represented by general formula (D) and / or the structural unit represented by general formula (S), the structural unit represented by general formula (AE) (the structural unit represented by general formula (DE) and / or the structural unit represented by general formula (SE)), and depending on the case, the structural unit represented by general formula (MA), the structural unit represented by general formula (E) and / or the structural unit represented by general formula (EE).

[0273] After step (III), in order to remove unwanted components other than the desired polymer (A), it is preferable to further perform the following steps.

[0274] First, the reaction solution, which has been diluted with an organic solvent and for which acid (e.g., formic acid, citric acid, etc.) has been added, is vigorously stirred for at least 3 minutes using a separatory funnel. It is then allowed to stand for at least 30 minutes to separate into an organic phase and an aqueous phase, and the aqueous phase is removed. This yields an organic solution of polymer (A).

[0275] An excess of toluene is added to the organic solution of the obtained polymer (A) to cause polymer (A) to redeprecipitate. Furthermore, the polymer powder obtained by redeprecipitation is further washed with toluene several times (e.g., twice).

[0276] In addition, to remove acidic or basic catalysts, the obtained polymer powder is repeatedly washed with ion-exchanged water multiple times (e.g., 3 times).

[0277] The polymer powder, after being washed with ion-exchanged water, is dried at 30–60°C for at least 16 hours to obtain the polymer (A) of this embodiment with high purity.

[0278] In this embodiment, it is also preferable to further add water to the polymer (A) in the same manner as in step (II') to open the ring of the structural unit of formula (MA) contained in the polymer (A) and generate the structural unit represented by formula (M). By means of this step, the solubility of the polymer (A) in solvents or the like can be adjusted.

[0279] (Polymer solution containing polymer (A))

[0280] The polymer solution of this embodiment contains the polymer (A) described above.

[0281] The polymer solution of this embodiment may contain a polymer (A) and a compound (B) having a thiol group and an alkoxy group or an oligomer thereof.

[0282] Compound (B) can use known compounds within the scope of the effects of the present invention, provided that it has a thiol group and an alkoxy group.

[0283] The polymer solution of this embodiment, by containing compound (B) or its oligomers, can provide a resin-cured product with excellent adhesion to substrates, etc. The substrate is not particularly limited, and examples, such as glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, and copper-clad laminates, can be described later.

[0284] In this embodiment, from the viewpoint of the effects of the present invention, the alkoxy group contained in compound (B) is preferably an alkoxy group having 1 to 3 carbon atoms, and it is also preferable to have a structure in which a thiol group and an alkoxy group are bonded to an organic chain that may contain one or more atoms selected from O, N, S, P and Si.

[0285] Specifically, compound (B) is preferably a compound represented by the following general formula (a).

[0286]

[0287] In general formula (a), R independently represents an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and at least two Rs are alkoxy groups having 1 to 3 carbon atoms.

[0288] L represents an m+n valence organic chain that may contain one or more atoms selected from O, N, S, P, and Si.

[0289] In this embodiment, examples of organic chains with an m+n valence of L include straight-chain or branched alkylene groups (m+n: 2) with 1 to 10 carbon atoms, m+n valence groups derived from straight-chain or branched alkanes with 1 to 20 carbon atoms, and m+n valence groups derived from substituted or unsubstituted siloxanes.

[0290] X represents a single bond or a divalent organic group that may contain a carbonyl, (thio)ester, or (thio)amide group.

[0291] In this embodiment, X is preferably a single bond or an alkylene ester group having 1 to 10 carbon atoms.

[0292] Q represents a single bond or a divalent organic group that may contain a carbonyl group, a (thio)ester group, or a (thio)amide group.

[0293] In this embodiment, Q is preferably a single bond or an alkylene ester group having 1 to 10 carbon atoms.

[0294] The m:n (molar ratio) is 1:1 to 1:8, and the m+n is 2 to 20.

[0295] The weight-average molecular weight of this compound is 100–2000.

[0296] Examples of compound (B) include 3-mercaptopropylmethyldimethoxysilane (KBM-802, manufactured by Shin-Etsu Silicone Co., Ltd.), 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Silicone Co., Ltd.), (3-mercaptopropyl)triethoxysilane, multifunctional silane coupling agents containing siloxane chains (KR-519, manufactured by Shin-Etsu Silicone Co., Ltd.), and multifunctional silane coupling agents containing organic chains having the following structural units.

[0297]

[0298] In the above general formula, the a:b (molar ratio) is 2:1 to 4:1. The weight-average molecular weight is 1000 to 1500. * represents a linking bond. Examples of this compound include X-12-1154 (manufactured by Shin-Etsu Silicone Co., Ltd.).

[0299] Moreover, compound (B) or its oligomers can be used alone or in combination of two or more.

[0300] In the polymer solution of this embodiment, from the viewpoint of the effects of the present invention, the compound (B) or its oligomer is 0.25 to 20% by mass relative to the polymer (A), preferably 1.0 to 15% by mass, and more preferably 2.0 to 12% by mass.

[0301] In addition, the polymer solution may contain at least one selected from polyfunctional (meth)acrylic acid compounds and monofunctional (meth)acrylic acid compounds, without affecting the effects of the present invention.

[0302] [Polyfunctional (meth)acrylic acid compounds]

[0303] Compounds having two or more (meth)acryloyl groups, i.e., polyfunctional (meth)acrylate compounds, can use conventionally known compounds as long as they can achieve the effects of the present invention.

[0304] Examples of polyfunctional (meth)acrylic acid compounds include, but are not limited to, compounds represented by the following general formulas (1b-p), (1c-p), and (1d-p).

[0305] k, R, X in general formula (1b-p) 1 X 1 'and X 2 The definition and specific method are the same as those in the general formula (1b) above. Furthermore, k, R, and X in general formula (1c-p) are... 1 X 2 X 3 X 4 X 5 and X 6 The definition and specific method are the same as those in the above general formula (1c).

[0306] In general formulas (1b-p), (1c-p), and (1d-p), Y is a hydrogen atom or a (meth)acryloyl group or a combination thereof.

[0307] Compounds in which Y is a hydrogen atom in general formulas (1b-p), (1c-p), and (1d-p) can be unreacted monomers (i.e., compounds represented by general formulas (1b-p), (1c-p), and (1d-p)) or can be added separately.

[0308] In the general formula (1d-p), n is an integer of 2 or more, preferably an integer of 2 to 5, and more preferably an integer of 2 to 3.

[0309]

[0310]

[0311] Specific examples of polyfunctional (meth)acrylic acid compounds represented by the general formula (1b-p) include compounds with the following structures, but are not limited to these. Additionally, in the following compounds, Y represents a hydrogen atom or a (meth)acryloyl group or a combination thereof.

[0312]

[0313] Specific examples of polyfunctional (meth)acrylic acid compounds represented by the general formula (1c-p) include the following compounds, but are not limited to these.

[0314]

[0315]

[0316] In the polymer solution of this embodiment, the above-mentioned polyfunctional (meth)acrylic acid compound can be incorporated within a range that does not affect the effect of the present invention. The amount of the peak area of ​​the polyfunctional (meth)acrylic acid compound in the gel permeation chromatography (GPC) chromatogram of the resin composition is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less relative to the peak area of ​​the resin.

[0317] [Monofunctional (meth)acrylic acid compounds]

[0318] The polymer solution of this embodiment may contain a compound having one (meth)acryloyl group, i.e., a monofunctional (meth)acrylic acid compound.

[0319] Examples of monofunctional (meth)acrylic acid compounds include those represented by the following general formula (Sa-m). Monofunctional (meth)acrylic acid compounds can be unreacted monomers or can be added separately.

[0320] In the general formula (Sa-m), regarding X 10 The definition of R is the same as that in the general formula (Sa).

[0321]

[0322] Specific examples of compounds represented by the general formula (Sa-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanediethanol 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.

[0323] In the polymer solution of this embodiment, a monofunctional (meth)acrylic acid compound can be incorporated within a range that does not affect the effect of the present invention. The amount of the peak area of ​​the monofunctional (meth)acrylic acid compound in the gel permeation chromatography (GPC) chromatogram of the resin composition is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less relative to the peak area of ​​the resin.

[0324] The polymer solution of this embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. One or more of the following can be used as the organic solvent: ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, etc.

[0325] Specific examples of organic solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, and cyclohexanone. These can be used alone or in combination of two or more.

[0326] The amount of organic solvent used is not particularly limited, and it is used in an amount where the concentration of the non-volatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0327] (Preparation of polymer solutions)

[0328] The polymer solution of this embodiment can be prepared by mixing the above-mentioned components using a known method. The polymer solution of this embodiment is used as a resin material in the photosensitive resin composition described below.

[0329] <Photosensitive Resin Composition>

[0330] The photosensitive resin composition of this embodiment contains the above-described polymer, a polyfunctional (meth)acrylic acid compound or a monofunctional (meth)acrylic acid compound added as needed, and a photosensitizer. That is, the photosensitive resin composition of this embodiment contains the polymer solution (varnish, resin composition) of this embodiment and the photosensitizer. Hereinafter, each component will be described.

[0331] [Photosensitive agent]

[0332] Photosensitive agents used in the photosensitive resin composition of this embodiment can be exemplified by photoradical polymerization initiators.As photoradical polymerization initiators, known compounds can be used, 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, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methylpropanone]-1,2-(dimethylamino)-2-[4-methylphenyl]-1-propanone-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)-1-propanone ...4-methylphenyl]-1-propanone-1-propanone-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-(dimethylamino)-2-[4-methylphenyl]-1-propanone-1 Alkylphenone compounds such as 1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone and 2-carboxybenzophenone; benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone compounds such as 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine. Halomethylated triazine compounds such as 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole; halomethylated oxadiazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1 Bimidazole compounds such as 2'-biimidazole and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethanone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime); diaceticotinamide compounds such as bis(n5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)-phenyl)titanium; benzoate ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine.Photoradical polymerization initiators can be used alone or in combination of two or more.

[0333] The photoradical polymerization initiator is used in an amount of 1 to 20 parts by weight relative to 100 parts by weight of the polymer, preferably in an amount of 3 to 10 parts by weight.

[0334] The photosensitive resin composition of this embodiment exhibits high sensitivity in photolithography and excellent alkali solubility due to the presence of the aforementioned components. Therefore, the photosensitive resin composition possesses excellent developability and processability in photolithography. Furthermore, since yellowing of the photosensitive resin composition is suppressed, the article obtained by curing this photosensitive resin composition is transparent.

[0335] In addition to the polymer, polyfunctional (meth)acrylic acid compound, and photosensitizer described above, the photosensitive resin composition of this embodiment may also contain a compound having one (meth)acryloyl group (a monofunctional (meth)acrylic acid compound). The monofunctional (meth)acrylic acid compound is the same as described above. By containing a monofunctional (meth)acrylic acid compound, the alkali solubility of the obtained photosensitive resin composition is further improved, and yellowing is reduced.

[0336] As one approach, the photosensitive resin composition may contain a colorant. By containing a colorant, it can be preferably used as a forming material for color filters in liquid crystal display devices or solid-state imaging elements. Various pigments or dyes can be used as colorants.

[0337] As a pigment, either organic or inorganic pigments can be used.

[0338] As organic pigments, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinacridone pigments, metal complex pigments, diketo-pyrrolo-pyrrole pigments, xanthene pigments, pyrromethene pigments, and dye lake pigments are all available.

[0339] As inorganic pigments, they can be white / extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), colored pigments (lead yellow, cadmium-based pigments, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, bengala, zinc chromate, lead oxide, ultramarine, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), brightening pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

[0340] As a dye, for example, known dyes described in Japanese Patent Application Publication No. 2003-270428, Japanese Patent Application Publication No. Hei 9-171108, Japanese Patent Application Publication No. 2008-50599, etc., can be used.

[0341] When a photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one colorant or two or more colorants.

[0342] Colorants (especially pigments) can be used with appropriate average particle size depending on the purpose or application. For example, when transparency is particularly required, such as in color filters, a small average particle size of less than 0.1 μm is preferred. In addition, when opacity is required, such as in coatings, a large average particle size of more than 0.5 μm is preferred.

[0343] Depending on the purpose or use, colorants can undergo surface treatments such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, and wax coating.

[0344] When a photosensitive resin composition contains a colorant, the amount can be set appropriately according to the purpose or use. However, from the viewpoint of balancing 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 amount of non-volatile components (components other than solvents) in the photosensitive resin composition.

[0345] (surfactant)

[0346] The photosensitive resin composition of this embodiment may contain a surfactant, preferably a nonionic surfactant.

[0347] By incorporating a nonionic surfactant, the coating properties of the photosensitive resin composition are improved when coated onto a substrate to obtain a resin film, resulting in a coating film of uniform thickness. Furthermore, it prevents residue or patterns from bubbling up during the development of the coating film.

[0348] Nonionic surfactants are, for example, compounds containing fluorinated groups (e.g., fluorinated alkyl groups) or silanol groups, or compounds with siloxane bonds as the main backbone. In this embodiment, surfactants containing fluorinated surfactants or silicone surfactants are more preferred as nonionic surfactants, and fluorinated surfactants are particularly preferred. Examples of fluorinated surfactants include MEGAFACE F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F-554, F-556 and F-557 manufactured by DIC Corporation, and Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited, but are not limited to these.

[0349] The amount of surfactant incorporated when using surfactant is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of resin.

[0350] (solvent)

[0351] Photosensitive resin compositions typically contain a solvent. Organic solvents are preferred as solvents. Specifically, one or more of ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, and carbonate solvents can be used.

[0352] Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl methanol (MIBC), γ-butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl n-pentyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof.

[0353] The amount of solvent used is not particularly limited, and it is used in an amount where the concentration of the non-volatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0354] (Sunscreen)

[0355] The resin composition of this embodiment can contain a light-blocking agent. The photosensitive resin composition may contain only one light-blocking agent or two or more light-blocking agents.

[0356] When a photosensitive resin composition contains a light-blocking agent, the amount of which can be appropriately set according to the purpose or use. However, from the viewpoint of balancing light-blocking performance and dispersion stability of the light-blocking agent, 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 amount of non-volatile components (components other than solvents) in the photosensitive resin composition.

[0357] (Cross-linking agent)

[0358] The photosensitive resin composition of this embodiment may contain a crosslinking agent.

[0359] Crosslinking agents are not particularly limited as long as they can crosslink polymers through the action of active chemical species generated from photopolymerization initiators (that can form chemical bonds with polymers).

[0360] Crosslinking agents can not only form chemical bonds with polymers, but can also react with each other to form bonds.

[0361] Crosslinking agents are preferably, for example, polyfunctional compounds having two or more polymerizable double bonds in one molecule, more preferably polyfunctional (meth)acrylic acid compounds having two or more (meth)acryloyl groups in one molecule (however, the crosslinking agent is not part of the polymer). From the viewpoint of uniform curing and further improved sensitivity, it is preferable to use a crosslinking agent having crosslinking groups of the same type as the crosslinking groups (polymerizable double bonds) of the polymer.

[0362] There is no particular upper limit to the number of functional groups (number of polymerizable double bonds) per molecule of the crosslinking agent, but it can be, for example, 8 or less, preferably 6 or less.

[0363] Specifically, crosslinking agents include: ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, cyclohexanediethanol dimethacrylate, bisphenol A alkylene oxide dimethacrylate, bisphenol F alkylene oxide dimethacrylate, trimethylolpropane trimethacrylate, dimethylolpropane tetramethacrylate, glycerol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, ethylene oxide addition trimethylolpropane trimethacrylate, ethylene oxide addition dimethylolpropane trimethacrylate, etc. 1,3-propane tetra(meth)acrylate, ethylene oxide addition pentaerythritol tetra(meth)acrylate, ethylene oxide addition dipentaerythritol hexa(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition ditrimethylolpropane tetra(meth)acrylate, propylene oxide addition pentaerythritol tetra(meth)acrylate, propylene oxide addition dipentaerythritol hexa(meth)acrylate, ε-caprolactone addition trimethylolpropane tri(meth)acrylate Multifunctional (meth)acrylates include ethyl methacrylates, ε-caprolactone-added di(trimethylolpropane)tetra(meth)acrylates, ε-caprolactone-added pentaerythritol tetra(meth)acrylates, and ε-caprolactone-added dipentaerythritol hexa(meth)acrylates; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, bisphenol A epoxy divinyl ether, etc. Phenolic F epoxy divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide addition trimethylolpropane trivinyl ether, ethylene oxide addition ditrimethylolpropane tetravinyl ether, ethylene oxide addition pentaerythritol tetravinyl ether, ethylene oxide addition dipentaerythritol hexavinyl ether and other multifunctional vinyl ethers;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-vinyloxycyclohexyl(meth)acrylate Ethyleneoxymethylcyclohexyl methyl ester, p-ethyleneoxymethylphenyl methyl methacrylate, 2-(ethyleneoxyethoxy)ethyl methacrylate, 2-(ethyleneoxyethoxyethoxyethoxy)ethyl methacrylate, and other (meth)acrylates containing vinyl ether groups; ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butanediol diallyl ether, hexanediol diallyl ether, bisphenol A epoxy diallyl ether, bisphenol F epoxy diallyl ether, etc. Multifunctional allyl ethers, including trimethylolpropane triallyl ether, dimethylolpropane tetraallyl ether, glycerol triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide addition trimethylolpropane triallyl ether, ethylene oxide addition dimethylolpropane tetraallyl ether, ethylene oxide addition pentaerythritol tetraallyl ether, ethylene oxide addition dipentaerythritol hexaallyl ether, and other polyfunctional allyl ethers; and allyl acrylates containing allyl groups, such as (meth)acrylates. ; isocyanurates containing polyfunctional (meth)acryloyl groups, such as tris(acryloyloxyethyl)isocyanurate, tris(methacryloyloxyethyl)isocyanurate, alkylene oxide tris(acryloyloxyethyl)isocyanurate, and alkylene oxide tris(methacryloyloxyethyl)isocyanurate; isocyanurates containing polyfunctional allyl groups, such as triallyl isocyanurate; polyfunctional urethane (meth)acrylates obtained by reacting polyfunctional isocyanates such as toluene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; and polyfunctional aromatic vinyl groups such as divinylbenzene.

[0364] Among them, the preferred are trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate.

[0365] When a photosensitive resin composition contains a crosslinking agent, the composition may contain only one type of crosslinking agent or two or more. The amount of the crosslinking agent can be appropriately set according to the purpose or application. For example, the amount of crosslinking agent relative to 100 parts by weight of the photosensitive resin composition is typically 30 to 70 parts by weight, and preferably around 40 to 60 parts by weight.

[0366] Photosensitive resin compositions may contain fillers, adhesive resins other than the polymers mentioned above, acid-producing agents, heat resistance modifiers, developing agents, plasticizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, matting agents, defoamers, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, thixotropic agents, thixotropic aids, silane coupling agents, polyvalent phenolic compounds, etc., depending on various purposes or required properties.

[0367] [Films, color filters, black matrices, liquid crystal displays, and solid-state imaging elements]

[0368] By forming a film using the aforementioned photosensitive resin composition and then exposing / developing the film to form a pattern, a patterned film can be obtained. This film is suitable for color filters or black matrices, etc. That is, by forming a pattern using a photosensitive resin composition containing a colorant, a color filter can be obtained. Furthermore, by forming a pattern using a photosensitive resin composition containing a light-blocking agent, a black matrix can be obtained. Then, a liquid crystal display device or a solid-state imaging element equipped with a color filter or a black matrix can be manufactured.

[0369] The typical steps for forming a pattern are explained.

[0370] (Formation of photosensitive resin film)

[0371] For example, the above-mentioned photosensitive resin composition is coated onto any substrate and dried as needed, thereby first obtaining a photosensitive resin film.

[0372] The substrate for coating the composition is not particularly limited. Examples include glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, and copper-clad laminates.

[0373] The substrate can be an unprocessed substrate or a substrate with electrodes or components formed on its surface. Surface treatment can be performed to improve adhesion.

[0374] The coating method for the photosensitive resin composition is not particularly limited. It can be carried out by spin coating using a spin coater, spray coating using a sprayer, impregnation, printing, roller coating, inkjet coating, etc.

[0375] Typically, heat treatment using heating plates, hot air, or ovens is employed to dry the photosensitive resin composition coated on a substrate. The heating temperature is usually 80–140°C, preferably 90–120°C. Furthermore, the heating time is usually 30–600 seconds, preferably around 30–300 seconds.

[0376] The thickness of the photosensitive resin film is not particularly limited and can be adjusted appropriately according to the desired final pattern. It is typically 0.5 to 10 μm, preferably 1 to 5 μm. In addition, the film thickness can be adjusted according to the solvent content in the photosensitive resin composition or the coating method, etc.

[0377] (exposure)

[0378] Exposure is typically achieved by shining active light onto a photosensitive resin film through a suitable photomask.

[0379] Examples of active light sources include X-rays, electron beams, ultraviolet light, and visible light. In terms of wavelength, light in the range of 200–500 nm is preferred. From the viewpoint of pattern resolution or operability, the light source is preferably gamma rays, h-rays, or i-rays from a mercury lamp, with i-rays being particularly preferred. Furthermore, two or more types of light can be mixed. As the exposure apparatus, a contact aligner, a mirror projection aligner, or a stepper is preferred.

[0380] The amount of light exposed can be adjusted appropriately based on the amount of photosensitizer in the photosensitive resin film, for example, 100–500 mJ / cm. 2 about.

[0381] Furthermore, after exposure, the photosensitive resin film can be reheated as needed (post-exposure baking). The temperature is, for example, 70–150°C, preferably 90–120°C. The time is, for example, 30–600 seconds, preferably 30–300 seconds. By performing post-exposure baking, the reaction is promoted by free radicals generated from the photoradical polymerization initiator, further accelerating the curing reaction.

[0382] (development)

[0383] By developing an exposed photosensitive resin film with a suitable developer, a pattern can be obtained, and a substrate with the pattern can be manufactured.

[0384] Since the photosensitive resin film formed from the photosensitive resin composition containing the polymer solution of this embodiment has excellent adhesion to the substrate, pattern peeling can be suppressed during the development process.

[0385] In the developing process, a suitable developer can be used, and methods such as immersion, puddle method, and spin coating can be employed for development. Through development, the exposed areas (positive cases) or unexposed areas (negative cases) of the photosensitive resin film are dissolved and removed, thereby obtaining a pattern.

[0386] There are no particular limitations on the developing solutions that can be used. For example, alkaline aqueous solutions or organic solvents can be used.

[0387] Specifically, examples of 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.

[0388] Because the polymer in this embodiment has adjusted alkali solubility and excellent sensitivity, it can make the pattern after exposure and development into the originally designed shape when using a strong alkaline developer such as TMAH (tetramethylammonium hydroxide) solution.

[0389] Specifically, examples of organic solvents include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) or butyl acetate, and ether solvents such as propylene glycol monomethyl ether.

[0390] Water-soluble organic solvents such as methanol and ethanol, or surfactants, can be added to the developer.

[0391] In this embodiment, an alkaline aqueous solution is preferably used as the developer, and more preferably, a tetramethylammonium hydroxide, sodium carbonate aqueous solution, or potassium hydroxide aqueous solution is used.

[0392] The concentration of the alkaline aqueous solution is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass.

[0393] Through the above processes, a pattern can be obtained / a patterned substrate can be manufactured, but various processing can be performed after development.

[0394] For example, after development, the pattern and substrate can be cleaned using a rinsing solution. Examples of rinsing solutions include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These can be used individually or in combination of two or more.

[0395] Furthermore, the obtained pattern can be heated to fully cure it. 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, for example, in the range of 15–300 minutes. This heat treatment can be performed using a heating plate, an oven, or a temperature-programmable oven. The ambient gas used during the heat treatment can be air, or inert gases such as nitrogen or argon. Moreover, heating can be performed under reduced pressure.

[0396] exist Figure 1 The diagram schematically illustrates a structural example of a liquid crystal display device and / or a solid-state imaging element equipped with a color filter and / or a black matrix.

[0397] A black matrix 11 and a color filter 12 are formed on the substrate 10. Furthermore, a protective film 13 and a transparent electrode layer 14 are provided on the upper part of the black matrix 11 and the color filter 12.

[0398] The substrate 10 is typically made of a light-transmitting material, such as polymers of polyester, polycarbonate, polyolefin, polysulfone, or cyclic olefins, in addition to glass. The substrate 10 may, as needed, be a substrate that has undergone corona discharge treatment, ozone treatment, or chemical treatment.

[0399] The substrate 10 is preferably made of glass.

[0400] Black matrix 11, for example, is composed of a cured product of a photosensitive resin composition containing a light-blocking agent.

[0401] As a color filter 12, there are usually three colors: red, green, and blue. The color filter 12 is composed of a cured product of a photosensitive resin composition containing a colorant corresponding to each color.

[0402] The embodiments of the present invention have been described above, but these are merely examples, and various configurations other than those described can be employed. Furthermore, the present invention is not limited to the above embodiments, and modifications and alterations within the scope of achieving the objectives of the present invention are included in the present invention.

[0403] Example

[0404] The present invention will now be described in further detail with reference to embodiments, but the present invention is not limited thereto.

[0405] The compounds used in the examples are sometimes referred to by the following abbreviations or trade names.

[0406] MA: Maleic anhydride.

[0407] NB: 2-norbornene.

[0408] MEK: Methyl ethyl ketone.

[0409] PEMP: Pentaerythritol tetra(3-mercaptopropionate), a compound represented by the following formula (s-2) (manufactured by SC Organic Chemical Co., Ltd.).

[0410]

[0411] TMMP: Trimethylolpropane tris(3-mercaptopropionate), a compound represented by the following formula (s-1) (manufactured by SC Organic Chemical Co., Ltd.).

[0412]

[0413] DPMP: Dipentaerythritol hexa(3-mercaptopropionate), a compound represented by the following formula (s-3) (manufactured by SC Organic Chemical Co., Ltd.).

[0414]

[0415] TEMPIC: Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, the compound represented by the following formula (s-5) (manufactured by SC Organic Chemical Co., Ltd.).

[0416]

[0417] Karenz MT PE-1: Pentaerythritol tetra(3-mercaptobutyrate), a compound represented by the following formula (s-9) (manufactured by Showa Denko KK).

[0418]

[0419] EGMP-4: Tetraethylene glycol bis(3-mercaptopropionate), a compound represented by the following formula (s-4) (manufactured by Showa Denko KK).

[0420]

[0421] TS-G: The compound represented by the following formula (s-11) (manufactured by Shikoku Chemicals Corporation).

[0422]

[0423] 3CTS-G: The compound represented by the following formula (s-12) (manufactured by Shikoku Chemicals Corporation).

[0424]

[0425] BTGL: Butyl mercaptoacetate, the compound represented by the following formula (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0426]

[0427] 4-HBA: 4-hydroxybutyl acrylate.

[0428] HEMA: 2-Hydroxyethyl methacrylate.

[0429] GMA: Glycidyl methacrylate.

[0430] A-TMM-3LM-N: A mixture of the following two compounds, with the amount of the left-hand compound in the mixture measured by gas chromatography being approximately 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0431]

[0432] A-9550: A mixture of the following two compounds, with the amount of the pentaacrylate compound on the left side of the mixture estimated based on the hydroxyl value to be approximately 50% (manufactured by Shin-Nakamura Chemical Co., Ltd.), hydroxyl value: 50 mg KOH / g.

[0433]

[0434] KBM-803: 3-Mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.).

[0435] <Synthesis of Raw Material Polymers>

[0436] (Synthesis of raw material polymer 1)

[0437] 602.56 g (451.92 g, 4.8 mol) of a 75% toluene solution of 2-norbornene, 470.69 g (4.8 mol) of maleic anhydride (MA), and 2238.50 g of methyl ethyl ketone (MEK) were added to a reaction vessel equipped with a stirrer, cooling pipe, and dropping funnel, and the mixture was stirred / dissolved. Next, dissolved oxygen in the system was removed by nitrogen bubbling, and the temperature was increased. When the internal temperature reached 80°C, a solution was added over a period of 1 hour, consisting of dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601, 44.21 g, 0.19 mol) and pentaerythritol tetra(3-mercaptopropionate) (PEMP, 140.73 g, 0.29 mol) dissolved in 189.74 g of MEK. Subsequently, the reaction was further carried out at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymer solution obtained above was added dropwise to 3686.4 g of methanol, causing a white solid to precipitate. The obtained white solid was further washed with 3686.4 g of methanol and then dried under vacuum at 120°C to obtain 908.1 g of a polymer (starting polymer 1) containing structural units derived from 2-norbornene and structural units derived from maleic anhydride.

[0438] The obtained polymer was measured using gel permeation chromatography (GPC), and the results showed that the weight-average molecular weight Mw was 2700 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.57.

[0439] [Structural Analysis of Raw Material Polymer 1]

[0440] In the synthesis of raw material polymer 1, the reaction began with monomers and PEMP dissolved in the solvent. Subsequently, the reaction progressed to produce the polymer. The reaction solution and the obtained polymer were analyzed, and the results are as follows.

[0441] (a) Analysis of the reaction solution

[0442] No peak of PEMP monomer was observed in the GPC measurement of the reaction solution before reprecipitation purification. That is, it was confirmed that no PEMP remained in the reaction solution. Moreover, in the GC (gas chromatography) measurement of the reaction solution before reprecipitation purification, it was confirmed that the peaks of 2-norbornene monomer and maleic anhydride monomer decreased in the reaction solution after the reaction compared with the unreacted state, indicating that 2-norbornene and maleic anhydride reacted to form a polymer.

[0443] The measurement conditions for gas chromatography are as follows.

[0444] GC device: GC-2030 (Shimadzu Corporation).

[0445] Carrier gas: N2.

[0446] Detector: Flame Ionization (FID) detector, FID temperature: 300℃.

[0447] Column: SH-RXi-1HT, inner diameter 0.25, length 30m, film thickness 0.25μm (Shimadzu GLC Ltd.).

[0448] Vaporization chamber temperature: 210℃.

[0449] Column flow rate: 0.64 mL / min.

[0450] The column heating conditions were as follows: hold at 50℃ for 5 minutes, increase the temperature to 300℃ at a rate of 20℃ / min, and hold at 300℃ for 10 minutes.

[0451] (b) Polymer analysis

[0452] In the GPC measurements of the reprecipitated and purified polymer, no peaks of PEMP monomer, 2-norbornene monomer, or maleic anhydride monomer were observed. That is, it was confirmed that no PEMP, 2-norbornene monomer, or maleic anhydride remained in the polymer.

[0453] The sulfur content in the raw material polymer 1 synthesized using PEMP was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in raw material polymer 1. Furthermore, in the raw material polymer 1... 13 In C-NMR measurements, a peak 'b' originating from carbon 'b' was confirmed near 62.0 ppm. That is, PEMP was confirmed to have been introduced into the polymer.

[0454] In (c) raw material polymer 1 13 In the C-NMR measurements, peak a, originating from carbon a of the PEMP monomer represented by chemical formula (i), was not identified. Instead, peak c, originating from carbon c corresponding to the sulfide (RS-R') of the raw material polymer 1 represented by chemical formula (ii), appeared. The integral value of peak c is approximately twice that of peak b.

[0455]

[0456] (The PEMP monomer represented by chemical formula (i)) 13C-NMR measurements confirmed peak a originating from carbon a at around 19.0 ppm and peak b originating from carbon b at around 62.0 ppm.

[0457]

[0458] (by means of the raw material polymer 1 represented by chemical formula (ii)) 13 C-NMR measurements confirmed a peak originating from carbon C around 28 ppm.

[0459] As can be seen from (a) and (b) above, the added PEMP, 2-norbornene monomer and maleic anhydride react and are introduced into the polymer.

[0460] Based on this content and the experimental results in (c) above, and further considering the above-mentioned raw materials (synthesis of raw material polymer 1), it can be seen that the molecular structure of raw material polymer 1 has the structure represented by the following general formula (I-1).

[0461]

[0462] (Where, A is a structural unit derived from 2-norbornene, represented by the following formula (NB-1), and X is a hydrogen atom. B' is a structural unit derived from maleic anhydride, represented by the following formula (MA).)

[0463]

[0464] The polymer synthesized using raw material polymer 1, which has this structure, also has the same structure.

[0465] 13 The conditions for C-NMR measurement are as follows.

[0466] (Test conditions) The measurement sample is prepared by adding the measurement solvent to the weighed sample to adjust the concentration, and then injecting the specified amount into the NMR measurement sample tube.

[0467] Measurement device: JNM-ECA400 superconducting FT-NMR instrument of JEOL Ltd.

[0468] Resonant frequency: 100.53MHz.

[0469] Measurement nucleus: 13 C.

[0470] Measurement method: NNE measurement (Inverse Gate Decoupling Method).

[0471] Pulse width: 3.83 μsec.

[0472] Pulse repetition waiting time: 30s.

[0473] Total number of times: 4096.

[0474] Temperature measured: Room temperature.

[0475] Measurement solvent: DMSO-d6 (deuterated dimethyl sulfoxide).

[0476] Sample concentration: 20% (w / v).

[0477] (Synthesis of raw material polymer 2)

[0478] 353.02 g (3.6 mol) of maleic anhydride, 338.94 g (3.6 mol) of 2-norbornene, and 41.45 g (0.180 mol) of dimethyl 2,2'-azobis(2-methylpropionic acid) were metered into a reaction vessel of appropriate size equipped with a stirrer and cooling pipe. These were dissolved in a mixed solvent consisting of 578.98 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution.

[0479] Nitrogen was bubbled through the solution for 30 minutes to remove oxygen. Then, the solution was heated at 63°C for 9.5 hours while stirring, thereby polymerizing maleic anhydride and 2-norbornene to produce a polymerization solution.

[0480] The polymerization solution obtained above was diluted with 712.92 g of methyl ethyl ketone and then added dropwise to 8519.9 g of methanol, thereby precipitating a white solid. The obtained white solid was dried under vacuum at 120 °C, thereby obtaining 550.4 g of polymer (raw material polymer 2) containing structural units derived from 2-norbornene and structural units derived from maleic anhydride.

[0481] The obtained polymer was measured by GPC, and the results showed that the weight-average molecular weight Mw was 11,600 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.79.

[0482] (Synthesis of raw material polymer 3)

[0483] 353.02 g (3.6 mol) of maleic anhydride, 338.94 g (3.6 mol) of 2-norbornene, and 33.16 g (0.144 mol) of dimethyl 2,2'-azobis(2-methylpropionic acid) were metered into a reaction vessel of appropriate size equipped with a stirrer and cooling pipe. These were dissolved in a mixed solvent consisting of 1030.1 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution.

[0484] Nitrogen was bubbled through the solution for 30 minutes to remove oxygen. Then, the solution was heated at 65°C for 1.5 hours with stirring, followed by further heating at 80°C for 6 hours, thereby polymerizing maleic anhydride and 2-norbornene to produce a polymer solution.

[0485] The polymerization solution obtained above was added dropwise to 8519.9 g of methanol, causing a white solid to precipitate. The obtained white solid was then vacuum dried at 120 °C to obtain 607.5 g of a polymer (raw material polymer 3) containing structural units derived from 2-norbornene and structural units derived from maleic anhydride.

[0486] The obtained polymer was measured using gel permeation chromatography (GPC), and the results showed that the weight-average molecular weight Mw was 7000 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.82.

[0487] (Synthesis of raw material polymer 4)

[0488] 602.56 g of a 75% toluene solution of 2-norbornene (equivalent to 451.92 g, 4.8 mol of 2-norbornene), maleic anhydride (MAN, 470.69 g, 4.8 mol), and 2281.74 g of methyl ethyl ketone (MEK) were added to a reaction vessel equipped with a stirrer, cooling pipe, and dropping funnel, and the mixture was stirred / dissolved. Next, dissolved oxygen in the system was removed by bubbling with nitrogen, and the temperature was increased. At an internal temperature of 80°C, a solution of 44.21 g, 0.19 mol of dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601) and 93.82 g, 0.19 mol of PEMP dissolved in 193.4 g of MEK was added over a period of 1 hour. The reaction was then further carried out at 80°C for 7 hours. Next, 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 further washed with 3686.4 g of methanol and then dried under vacuum at 120 °C to obtain 910.1 g of polymer (starting polymer 4) having structural units derived from 2-norbornene and structural units derived from maleic anhydride.

[0489] The obtained raw material polymer 4 was measured using gel permeation chromatography (GPC), and the results showed that the weight-average molecular weight Mw was 3500 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.62.

[0490] The sulfur content in the obtained polymer was confirmed by elemental analysis based on flask combustion and ion chromatography, confirming the presence of sulfur in the polymer.

[0491] In the GPC measurement of the reaction solution, no peak of PEMP monomer was observed, and no unreacted PEMP remained, thus confirming that PEMP was introduced into the raw material polymer 4.

[0492] Moreover, through the raw material polymer 4 13 C-NMR measurements confirmed that PEMP was introduced into the feed polymer 4.

[0493] Elemental analysis was performed, and the results showed that the sulfur content in raw material polymer 4 was 2.4 wt%.

[0494] (Synthesis of raw material polymer 5)

[0495] Except that TMMP (101.99 g, 0.25 mol) was used instead of PEMP, a polymer (raw material polymer 5) of 900.1 g with structural units derived from 2-norbornene and structural units derived from maleic anhydride was obtained in the same manner as raw material polymer 4.

[0496] The obtained raw material polymer 5 was measured using gel permeation chromatography (GPC), and the results showed that the weight-average molecular weight Mw was 3100 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.74.

[0497] In the GPC measurement of the reaction solution, no peak of TMMP monomer was observed, and no unreacted TMMP remained, thus confirming that TMMP was introduced into the raw material polymer 5.

[0498] Moreover, through the raw material polymer 5 13 C-NMR measurements confirmed that TMMP was introduced into the feed polymer 5.

[0499] The sulfur content in the obtained polymer was confirmed by using flask combustion and ion chromatography for elemental analysis, thus confirming the presence of sulfur in the polymer.

[0500] (Synthesis of raw material polymer 6)

[0501] Except that DPMP (100.23 g, 0.13 mol) was used instead of PEMP, a polymer (raw material polymer 6) of 890.2 g was obtained in the same manner as raw material polymer 4, which has structural units derived from 2-norbornene and structural units derived from maleic anhydride.

[0502] The obtained raw material polymer 6 was measured using gel permeation chromatography (GPC), and the results showed that the weight-average molecular weight Mw was 3600 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.02.

[0503] No peak of DPMP monomer was observed in the GPC measurement of the reaction solution, and no unreacted DPMP remained, thus confirming that DPMP was introduced into the raw material polymer 6.

[0504] Moreover, through the raw material polymer 6 13 C-NMR measurements confirmed that DPMP was introduced into the feed polymer 6.

[0505] The sulfur content in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the polymer.

[0506] (Synthesis of raw material polymer 7)

[0507] Except that TEMPIC (134.53 g, 0.25 mol) was used instead of PEMP, 879.9 g of polymer (raw material polymer 7) containing structural units derived from 2-norbornene and structural units derived from maleic anhydride was obtained in the same manner as raw material polymer 4.

[0508] The obtained raw material polymer 7 was measured using gel permeation chromatography (GPC), and the results showed that the weight-average molecular weight Mw was 2900 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.30.

[0509] In the GPC measurement of the reaction solution, no peak of TEMPIC monomer was observed, and no unreacted TEMPIC remained, thus confirming that TEMPIC was introduced into the raw material polymer 7.

[0510] Moreover, through the raw material polymer 7 13 C-NMR measurements confirmed that TEMPIC was introduced into the feed polymer 7.

[0511] The sulfur content in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the polymer.

[0512] (Synthesis of raw material polymer 8)

[0513] 50.21 g of a 75% toluene solution of 2-norbornene (equivalent to 37.66 g, 0.400 mol of 2-norbornene), 39.22 g, 0.400 mol of maleic anhydride (MAN), and 189.32 g of methyl ethyl ketone (MEK) were added to a reaction vessel equipped with a stirrer, cooling pipe, and dropping funnel, and the mixture was stirred / dissolved. Next, dissolved oxygen in the system was removed by bubbling with nitrogen, and the temperature was increased. At an internal temperature of 80°C, a solution of 3.68 g, 0.016 mol of dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601) and 8.72 g, 0.016 mol of KarenzMT (registered trademark) PE1 dissolved in 15.75 g of MEK was added over a period of 1 hour. The reaction was then further carried out at 80°C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 1228.8 g of methanol, causing a white solid to precipitate. The obtained white solid was further washed with 307.2 g of methanol and then dried under vacuum at 120 °C to obtain 64.5 g of a polymer (starting polymer 8) containing structural units derived from 2-norbornene and structural units derived from maleic anhydride. The obtained starting polymer 8 was measured using gel permeation chromatography (GPC), and the results showed that the weight-average molecular weight Mw was 2800 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.45.

[0514] In the GPC measurement of the reaction solution, no peak of Karenz MT PE1 monomer was observed, and no unreacted Karenz MT PE1 remained, thus confirming that Karenz MT PE1 was introduced into the raw material polymer 8.

[0515] Moreover, through the raw material polymer 8 13 C-NMR measurements confirmed that Karenz MT PE1 was introduced into the feed polymer 8.

[0516] The sulfur content in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the polymer.

[0517] (Synthesis of raw material polymer 9)

[0518] 50.21 g of a 75% toluene solution of 2-norbornene (equivalent to 37.66 g, 0.400 mol of 2-norbornene), 39.22 g, 0.400 mol of maleic anhydride (MAN), and 202.18 g of methyl ethyl ketone (MEK) were added to a reaction vessel equipped with a stirrer, cooling pipe, and dropping funnel, and the mixture was stirred / dissolved. Next, dissolved oxygen in the system was removed by bubbling with nitrogen, and the temperature was increased. At an internal temperature of 80°C, a solution of 3.68 g, 0.016 mol of dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601) and 11.90 g, 0.032 mol of EGMP-4 dissolved in 16.23 g of MEK was added over a period of 1 hour. The reaction was then further carried out at 80°C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 1228.8 g of methanol to precipitate a white solid. The obtained white solid was further washed with 307.2 g of methanol and then dried under vacuum at 120 °C to obtain 64.5 g of polymer (starter polymer 9) having structural units derived from 2-norbornene and structural units derived from maleic anhydride.

[0519] The obtained raw material polymer 9 was measured using gel permeation chromatography (GPC), and the results showed that the weight-average molecular weight Mw was 2900 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.57.

[0520] In the GPC measurement of the reaction solution, no peak of EGMP-4 monomer was observed, and no unreacted EGMP-4 remained, thus confirming that EGMP-4 was introduced into the raw material polymer 9.

[0521] Moreover, through the raw material polymer 9 13 C-NMR measurements confirmed that EGMP-4 was introduced into the feed polymer 9.

[0522] The sulfur content in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the polymer.

[0523] (Synthesis of raw material polymer 10)

[0524] Except that TS-G (73.45 g, 0.19 mol) was used instead of PEMP, 860.23 g of a polymer (raw material polymer 10) containing structural units derived from 2-norbornene and structural units derived from maleic anhydride was obtained in the same manner as raw material polymer 4.

[0525] The obtained raw material polymer 10 was measured using gel permeation chromatography (GPC), and the results showed that the weight-average molecular weight Mw was 3300 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.65.

[0526] In the GPC measurement of the reaction solution, no peak of TS-G monomer was observed, and no unreacted TS-G remained, thus confirming that TS-G was introduced into the raw material polymer 10.

[0527] Moreover, through the raw material polymer 10 13 C-NMR measurements confirmed that TS-G was introduced into the raw material polymer 10.

[0528] The sulfur content in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the polymer.

[0529] (Synthesis of raw material polymer 11)

[0530] Except that 3CTS-G (84.23 g, 0.19 mol) was used instead of PEMP, a polymer (raw material polymer 11) of 900.1 g with structural units derived from 2-norbornene and structural units derived from maleic anhydride was obtained in the same manner as raw material polymer 4.

[0531] The obtained raw material polymer 11 was measured using gel permeation chromatography (GPC), and the results showed that the weight-average molecular weight Mw was 3100 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.61.

[0532] In the GPC measurement of the reaction solution, no peak of 3CTS-G monomer was observed, and no unreacted 3CTS-G remained, thus confirming that 3CTS-G was introduced into the raw material polymer 11.

[0533] Moreover, through the raw material polymer 11 13 C-NMR measurements confirmed that 3CTS-G was introduced into the raw material polymer 11.

[0534] The sulfur content in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the polymer.

[0535] (Synthesis of raw material polymer 12)

[0536] Except that BTGL (113.83 g, 0.76 mol) was used instead of PEMP, a polymer (starter polymer 12) of 867.1 g was obtained in the same manner as starter polymer 4, having structural units derived from 2-norbornene and structural units derived from maleic anhydride.

[0537] The obtained raw material polymer 12 was measured using gel permeation chromatography (GPC), and the results showed that the weight-average molecular weight Mw was 2900 and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.57.

[0538] In the GPC measurement of the reaction solution, no peak of BTGL monomer was observed, and no unreacted BTGL remained, thus confirming that BTGL was introduced into the raw material polymer 12.

[0539] Moreover, through the raw material polymer 12 13 C-NMR measurements confirmed that BTGL was introduced into the raw material polymer 12.

[0540] The sulfur content in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the polymer.

[0541] [Example 1]

[0542] (Polymer Synthesis)

[0543] Polymer P1 was prepared by ring-opening of the MA unit of raw polymer 1 using a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic acid compound (4-HBA), followed by reaction with an epoxy-containing (meth)acrylic acid compound (GMA). The details are described below.

[0544] First, a solution was prepared by adding 100.54 g of MEK to 60 g (0.312 mol MA equivalent) of the starting polymer 1. Next, 58.12 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the reaction was carried out at 70°C for 2 hours. Then, 40.51 g (0.281 mol) of 4-HBA was further added, and the reaction was carried out at 70°C for 4 hours. Finally, 26.62 g (0.187 mol) of GMA was added, and the reaction was carried out at 70°C for 4 hours, thus preparing the reaction solution.

[0545] The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. Subsequently, the polymer was purified by the following steps.

[0546] The polymer was reprecipitated by using an excess of toluene.

[0547] The polymer powder obtained by reprecipitation was washed twice with an excess of toluene.

[0548] The polymer powder that had been washed twice was washed three times with excessive water.

[0549] The obtained reaction product was dried at 40°C for 16 hours.

[0550] Through the above, polymer P1 was obtained by using A-TMM-3LM-N and 4-HBA to open the ring of the structural units derived from maleic anhydride in the raw material polymer and reacting them with GMA.

[0551] GPC measurements of polymer P1 confirmed the disappearance of peaks from the polyfunctional (meth)acrylic acid compounds, monofunctional (meth)acrylic acid compounds, and epoxy-containing (meth)acrylic acid compounds used. This confirmed that the obtained polymer P1 did not contain unreacted (meth)acrylic acid compounds, (meth)acrylic acid compounds without hydroxyl groups, or unreacted epoxy-containing (meth)acrylic acid compounds.

[0552] Table 1 shows the components used in the synthesis example and the amount of each component, converted to maleic anhydride (MA), and by... 1 The amount (mole fraction, mol%) of each structural unit was calculated by H-NMR integral analysis and expressed in maleic anhydride (MA) conversion.

[0553] exist Figure 2 The figure shows polymer P1 1 H-NMR spectra, in Figure 3 The image shows a magnified view of the peak near 6.0 ppm.

[0554] Besides appearing Figure 3 polymer P1 1 In addition to the peak corresponding to the 3H of acryloyl group (-CH=CH2) at 5.8-6.7 ppm shown in the ¹H-NMR spectrum, peaks corresponding to the 2H of methacryloyl group (-C(CH3)=CH2) at 5.6-5.8 ppm and 6.0-6.1 ppm (indicated by ×) also appeared. In the GPC measurement of polymer P1, no peaks of unreacted trifunctional (meth)acrylic acid compound (A-TMM-3LM-N), monofunctional (meth)acrylic acid compound (4-HBA), or epoxy-containing (meth)acrylic acid compound (GMA) were observed, indicating that acryloyl group and methacryloyl group derived from GMA were introduced into the polymer.

[0555] Furthermore, in the GPC measurements of the reaction solutions before and after the ring-opening reaction and before and after the GMA addition reaction, the peaks originating from the trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) decreased before and after the ring-opening reaction, and the peaks originating from GMA decreased before and after the GMA addition reaction. This also indicates that A-TMM-3LM-N and GMA were introduced into the polymer.

[0556] (Preparation of polymer solutions)

[0557] 100 parts by mass of the obtained polymer P1 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution 1 with a solid content of 30% by mass.

[0558] (Preparation of photosensitive resin composition)

[0559] The following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a photosensitive resin composition 1, wherein the total solids concentration was 30% by mass.

[0560] Solid component (polymer P1) in polymer solution 1: 100 parts by mass.

[0561] Multifunctional acrylate (dipentaerythritol hexaacrylate) (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by weight.

[0562] Photopolymerization initiator (manufactured by BASF, Ingacure OXE01): 5 parts by weight.

[0563] Adhesive additive (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by weight.

[0564] Surfactant (manufactured by DIC Corporation, F-556): 0.5 parts by weight.

[0565] The obtained photosensitive resin composition was filtered as needed using a PTFE membrane filter Millex-LS (manufactured by Merck Millipore) to remove insoluble components.

[0566] [Example 2]

[0567] Except for changing the amount of 4-HBA added to 54.02 g, GMA to 33.28 g, and MEK to 100.91 g, polymer P2 was prepared in the same manner as in Example 1, and polymer solution 2 containing polymer P2 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0568] [Example 3]

[0569] Except for changing the amount of 4-HBA added to 56.27 g and MEK to 100.14 g, polymer P3 was prepared in the same manner as in Example 1, and polymer solution 3 containing polymer P3 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0570] [Example 4]

[0571] Except for changing the amount of 4-HBA added to 27.01 g and MEK to 102.93 g, polymer P4 was prepared in the same manner as in Example 1, and polymer solution 4 containing polymer P4 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0572] [Example 5]

[0573] Except for changing the amount of 4-HBA added to 56.27 g, GMA to 39.94 g, and MEK to 101.01 g, polymer P5 was prepared in the same manner as in Example 1, and polymer solution 5 containing polymer P5 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0574] [Example 6]

[0575] (Polymer Synthesis)

[0576] Polymer P6 was prepared by ring-opening of the MA unit of raw polymer 1 using a monofunctional (meth)acrylic acid compound (HEMA), followed by reaction with an epoxy-containing (meth)acrylic acid compound (GMA). Details are described below.

[0577] First, a solution was prepared by adding 112.76 g of MEK to 60 g (0.312 mol MA equivalent) of the starting polymer 1. Next, 25.38 g (0.195 mol) of HEMA was added to the solution, followed by 6.00 g (0.059 mol) of triethylamine, and the reaction was carried out at 70°C for 6 hours. Subsequently, 26.62 g (0.187 mol) of GMA was added, and the reaction was carried out at 70°C for 4 hours to prepare the reaction solution.

[0578] The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. Subsequently, the polymer was purified by the following steps.

[0579] Use excess water to cause the polymer to reprecipitate.

[0580] The polymer powder obtained by washing with excess water and then re-precipitating was repeatedly subjected to the process twice.

[0581] The obtained reaction product was dried at 40°C for 16 hours.

[0582] Through the above, polymer P6 was obtained by using HEMA to open the ring of the maleic anhydride-derived structural units in the raw material polymer and reacting them with GMA.

[0583] GPC measurements of polymer P6 confirmed the disappearance of both the peaks of the monofunctional (meth)acrylic acid compound and the peaks of the epoxy-containing (meth)acrylic acid compound. This confirmed that the obtained polymer P6 contained neither unreacted (meth)acrylic acid compounds nor epoxy-containing (meth)acrylic acid compounds.

[0584] Table 1 shows the components used in the synthesis example and the amount of each component, converted to maleic anhydride (MA), and by... 1 The amount (mole fraction, mol%) of each structural unit was calculated by H-NMR integral analysis and expressed in maleic anhydride (MA) conversion.

[0585] By 1 H-NMR measurements confirmed that polymer P6 has a ring-opening structure with HEMA and a structure that has reacted with GMA.

[0586] A polymer solution 6 containing polymer P6 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0587] [Example 7]

[0588] A polymer solution 7 with a solid content of 30% by mass was prepared by dissolving 100 parts by mass of polymer P1 obtained in Example 1 and 5 parts by mass of KBM-803 in propylene glycol monomethyl ether acetate (PGMEA). The photosensitive resin composition was prepared in the same manner as in Example 1.

[0589] [Example 8]

[0590] A polymer solution 8 with a solid content of 30% by mass was prepared by dissolving 100 parts by mass of polymer P2 obtained in Example 2 and 5 parts by mass of KBM-803 in propylene glycol monomethyl ether acetate (PGMEA). The photosensitive resin composition was prepared in the same manner as in Example 1.

[0591] [Example 9]

[0592] A polymer solution 9 with a solid content of 30% by mass was prepared by dissolving 100 parts by mass of polymer P3 obtained in Example 3 and 5 parts by mass of KBM-803 in propylene glycol monomethyl ether acetate (PGMEA). The photosensitive resin composition was prepared in the same manner as in Example 1.

[0593] [Example 10]

[0594] A polymer solution 10 with a solid content of 30% by mass was prepared by dissolving 100 parts by mass of polymer P4 obtained in Example 4 and 5 parts by mass of KBM-803 in propylene glycol monomethyl ether acetate (PGMEA). The photosensitive resin composition was prepared in the same manner as in Example 1.

[0595] [Example 11]

[0596] A polymer solution 11 with a solid content of 30% by mass was prepared by dissolving 100 parts by mass of polymer P5 obtained in Example 5 and 5 parts by mass of KBM-803 in propylene glycol monomethyl ether acetate (PGMEA). The photosensitive resin composition was prepared in the same manner as in Example 1.

[0597] [Example 12]

[0598] (Polymer Synthesis)

[0599] Polymer P10 was prepared by ring-opening of the MA unit of raw polymer 1 using a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N), followed by reaction with an epoxy-containing (meth)acrylic acid compound (GMA). Details are described below.

[0600] First, 100.57 g of MEK was added to 60 g (0.312 mol MA) of the starting polymer 1 to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to the solution, followed by 18.00 g (0.178 mol) of triethylamine, and the reaction was carried out at 70°C for 2 hours. Subsequently, 13.31 g (0.094 mol) of GMA was added, and the reaction was carried out at 70°C for 4 hours to prepare a reaction solution.

[0601] The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. Subsequently, the polymer was purified by the following steps.

[0602] The polymer was reprecipitated by using an excess of toluene.

[0603] The polymer powder obtained by reprecipitation was washed twice with an excess of toluene.

[0604] The polymer powder that had been washed twice was washed three times with excessive water.

[0605] The obtained reaction product was dried at 40°C for 16 hours.

[0606] Through the above, polymer P10 was obtained by using A-TMM-3LM-N to open the ring of the maleic anhydride-derived structural unit in the raw material polymer and reacting it with GMA.

[0607] GPC measurements of polymer P10 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic acid compound and the epoxy-containing (meth)acrylic acid compound used. This confirmed that the obtained polymer P10 did not contain unreacted (meth)acrylic acid compounds, (meth)acrylic acid compounds without hydroxyl groups, or unreacted epoxy-containing (meth)acrylic acid compounds.

[0608] By 1 H-NMR measurements confirmed that polymer P10 has a ring-opening structure with A-TMM-3LM-N and a structure that has reacted with GMA.

[0609] A polymer solution 12 containing polymer P10 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0610] [Example 13]

[0611] (Polymer Synthesis)

[0612] Polymer P12 was prepared by ring-opening of the MA unit of raw polymer 4 using a 5-functional (meth)acrylic acid compound (A-9550) and a monofunctional (meth)acrylic acid compound (4-HBA), followed by reaction with an epoxy-containing (meth)acrylic acid compound (GMA). The details are described below.

[0613] First, a solution was prepared by adding 100.57 g of MEK to 60 g (0.312 mol MA equivalent) of the starting polymer 4. Next, 70.06 g of A-9550 was added to the solution, followed by 18.00 g (0.178 mol) of triethylamine, and the reaction was carried out at 70°C for 2 hours. Then, 56.27 g (0.390 mol) of 4-HBA was added, and the reaction was carried out at 70°C for 4 hours. Finally, 26.62 g (0.187 mol) of GMA was added, and the reaction was carried out at 70°C for 4 hours, thus preparing the reaction solution.

[0614] The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. Subsequently, the polymer was purified by the following steps.

[0615] The polymer was reprecipitated by using an excess of toluene.

[0616] The polymer powder obtained by reprecipitation was washed twice with an excess of toluene.

[0617] The polymer powder that had been washed twice was washed three times with excessive water.

[0618] The obtained reaction product was dried at 40°C for 16 hours.

[0619] Through the above, polymer P12 was obtained by using A-9550 and 4-HBA to open the ring of the maleic anhydride-derived structural units in the raw material polymer and reacting them with GMA.

[0620] GPC measurements of polymer P12 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic acid compound, monofunctional (meth)acrylic acid compound, and epoxy-containing (meth)acrylic acid compound used. This confirmed that the obtained polymer P12 did not contain unreacted (meth)acrylic acid compounds, (meth)acrylic acid compounds without hydroxyl groups, or unreacted epoxy-containing (meth)acrylic acid compounds.

[0621] Table 1 shows the components used in the synthesis example and the amount of each component, converted to maleic anhydride (MA), and by... 1The amount (mole fraction, mol%) of each structural unit was calculated by H-NMR integral analysis and expressed in maleic anhydride (MA) conversion.

[0622] By 1 H-NMR measurements confirmed that polymer P12 has a ring-opening structure with A-9550 and 4-HBA and a structure that has reacted with GMA.

[0623] A polymer solution 13 containing polymer P12 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0624] [Example 14]

[0625] (Polymer Synthesis)

[0626] Polymer P13 was prepared by ring-opening the MA unit of the starting polymer 4 using a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N), followed by ring-opening through reaction with water, and then reacting with an epoxy-containing (meth)acrylic acid compound (GMA). Details are described below.

[0627] First, a solution was prepared by adding 100.57 g of MEK to 60 g (0.312 mol MA equivalent) of the starting polymer 4. Next, 58.12 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the reaction was carried out at 70°C for 2 hours. Then, 0.90 g (0.050 mol) of water was added, and the reaction was carried out at 70°C for 2 hours. Finally, 26.62 g (0.187 mol) of GMA was added, and the reaction was carried out at 70°C for 4 hours to prepare the reaction solution.

[0628] The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. Subsequently, the polymer was purified by the following steps.

[0629] The polymer was reprecipitated by using an excess of toluene.

[0630] The polymer powder obtained by reprecipitation was washed twice with an excess of toluene.

[0631] The polymer powder that had been washed twice was washed three times with excessive water.

[0632] The obtained reaction product was dried at 40°C for 16 hours.

[0633] Through the above, polymer P13 was obtained by using A-TMM-3LM-N and water to open the ring of the structural units derived from maleic anhydride in the raw material polymer and reacting them with GMA.

[0634] GPC measurements of polymer P13 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic acid compound and the epoxy-containing (meth)acrylic acid compound used. This confirmed that the obtained polymer P13 did not contain unreacted (meth)acrylic acid compounds, (meth)acrylic acid compounds without hydroxyl groups, or unreacted epoxy-containing (meth)acrylic acid compounds.

[0635] Table 1 shows the components used in the synthesis example and the amount of each component, converted to maleic anhydride (MA), and by... 1 The amount (mole fraction, mol%) of each structural unit was calculated by H-NMR integral analysis and expressed in maleic anhydride (MA) conversion.

[0636] By 1 H-NMR measurements confirmed that polymer P13 has a ring-opening structure with A-TMM-3LM-N and water, as well as a structure that has reacted with GMA.

[0637] A polymer solution 14 containing polymer P13 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0638] [Example 15]

[0639] (Polymer Synthesis)

[0640] A polymer was prepared by ring-opening the MA unit of the starting polymer 4 using a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N), followed by reaction with an epoxy-containing (meth)acrylic acid compound (GMA). Furthermore, polymer P14 was obtained by ring-opening the MA unit through a reaction with water. Details are described below.

[0641] First, a solution was prepared by adding 99.23 g of MEK to 60 g (0.312 mol MA equivalent) of the starting polymer 4. Next, 58.12 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the reaction was carried out at 70°C for 2 hours. Subsequently, 19.97 g (0.140 mol) of GMA was added, and the reaction was carried out at 70°C for 4 hours to prepare the reaction solution.

[0642] The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. Subsequently, the polymer was purified by the following steps.

[0643] The polymer was reprecipitated by using an excess of toluene.

[0644] The polymer powder obtained by reprecipitation was washed twice with an excess of toluene.

[0645] The polymer powder that had been washed twice was washed three times with excessive water.

[0646] The obtained reaction product was dried at 40°C for 16 hours.

[0647] Next, the polymer was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution with a solid content of 30% by mass. Water, at 30% by mass relative to the polymer solid content, was added to this polymer solution, and the reaction was carried out at 70°C for 5 hours. The resulting solution was then subjected to solvent displacement via the following steps.

[0648] Solvent replacement: PGMEA was added to the reaction mixture to achieve a solids concentration of 18% by mass, and the mixture was stirred until homogeneous. Solvent removal was then performed using a rotary evaporator at 50°C under reduced pressure. The solvent removal process was stopped after confirming a solids concentration of 27 ± 2% by mass using a heated drying moisture meter. This process was repeated twice more: adding PGMEA to achieve a solids concentration of 18% by mass and mixing until homogeneous; then removing the solvent under reduced pressure at 50°C; and adjusting the solids concentration to 27 ± 2% by mass using a heated drying moisture meter. Subsequently, solvent removal was performed to achieve a solids concentration of 30 ± 3% by mass, or PGMEA was added and stirred until homogeneous. Through these processes, water used in the reaction was removed, and the solvent was replaced with PGMEA.

[0649] Through the above, a polymer solution 15 was obtained containing polymer P14, which is obtained by ring-opening of the structural unit derived from maleic anhydride in the raw material polymer using A-TMM-3LM-N and reacting it with GMA, and then ring-opening of the MA unit by reaction with water.

[0650] GPC measurements of polymer P14 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic acid compound and the epoxy-containing (meth)acrylic acid compound used. This confirmed that the obtained polymer P14 did not contain unreacted (meth)acrylic acid compounds, (meth)acrylic acid compounds without hydroxyl groups, or unreacted epoxy-containing (meth)acrylic acid compounds.

[0651] The photosensitive resin composition was prepared in the same manner as in Example 1.

[0652] [Example 16]

[0653] (Polymer Synthesis)

[0654] Except that raw material polymer 5 was used instead of raw material polymer 1, polymer P15 was prepared in the same manner as in Example 3 by opening the MA unit of raw material polymer 5 with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic acid compound (4-HBA), and then reacting it with an epoxy-containing (meth)acrylic acid compound (GMA) to obtain polymer P15.

[0655] A polymer solution 16 containing polymer P15 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0656] [Example 17]

[0657] (Polymer Synthesis)

[0658] Except that raw material polymer 6 was used instead of raw material polymer 1, polymer P16 was prepared in the same manner as in Example 3 by opening the MA unit of raw material polymer 6 with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic acid compound (4-HBA), and then reacting it with an epoxy-containing (meth)acrylic acid compound (GMA) to obtain polymer P16.

[0659] A polymer solution 17 containing polymer P16 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0660] [Example 18]

[0661] (Polymer Synthesis)

[0662] Except that raw material polymer 7 was used instead of raw material polymer 1, polymer P17 was prepared in the same manner as in Example 3 by opening the MA unit of raw material polymer 7 with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic acid compound (4-HBA), and then reacting it with an epoxy-containing (meth)acrylic acid compound (GMA) to obtain polymer P17.

[0663] A polymer solution 18 containing polymer P17 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0664] [Example 19]

[0665] (Polymer Synthesis)

[0666] Except that raw material polymer 8 was used instead of raw material polymer 1, polymer P18 was prepared in the same manner as in Example 3, using ring-opening of the MA unit of raw material polymer 8 (a trifunctional (meth)acrylate compound (A-TMM-3LM-N) and monofunctional (meth)acrylate compound (4-HBA), followed by reaction with an epoxy-containing (meth)acrylate compound (GMA) to obtain polymer P18. Polymer solution 19 containing polymer P18 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0667] [Example 20]

[0668] (Polymer Synthesis)

[0669] Except that raw material polymer 9 was used instead of raw material polymer 1, polymer P19 was prepared in the same manner as in Example 3 by opening the MA unit of raw material polymer 9 with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic acid compound (4-HBA), and then reacting it with an epoxy-containing (meth)acrylic acid compound (GMA) to obtain polymer P19.

[0670] A polymer solution 20 containing polymer P19 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0671] [Example 21]

[0672] (Polymer Synthesis)

[0673] Except that raw material polymer 10 was used instead of raw material polymer 1, polymer P20 was prepared in the same manner as in Example 3 by opening the MA unit of raw material polymer 10 with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic acid compound (4-HBA), and then reacting it with an epoxy-containing (meth)acrylic acid compound (GMA) to obtain polymer P20.

[0674] A polymer solution 21 containing polymer P20 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0675] [Example 22]

[0676] (Polymer Synthesis)

[0677] Except that raw material polymer 11 was used instead of raw material polymer 1, polymer P21 was prepared in the same manner as in Example 3 by opening the MA unit of raw material polymer 11 with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic acid compound (4-HBA), and then reacting it with an epoxy-containing (meth)acrylic acid compound (GMA) to obtain polymer P21.

[0678] A polymer solution 22 containing polymer P21 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0679] [Comparative Example 1]

[0680] (Polymer Synthesis)

[0681] Polymer P7 was prepared by ring-opening of the MA unit of raw polymer 2 using a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic acid compound (4-HBA), followed by reaction with an epoxy-containing (meth)acrylic acid compound (GMA). The details are described below.

[0682] First, a solution was prepared by adding 102.93 g of MEK to 60 g (0.312 mol MA equivalent) of the starting polymer 2. Next, 58.12 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the reaction was carried out at 70°C for 2 hours. Then, 27.12 g (0.187 mol) of 4-HBA was added, and the reaction was carried out at 70°C for 4 hours. Finally, 26.62 g (0.187 mol) of GMA was added, and the reaction was carried out at 70°C for 4 hours, thus preparing the reaction solution.

[0683] The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. Subsequently, the polymer was purified by the following steps.

[0684] The polymer was reprecipitated by using an excess of toluene.

[0685] The polymer powder obtained by reprecipitation was washed twice with an excess of toluene.

[0686] The polymer powder that had been washed twice was washed three times with excessive water.

[0687] The obtained reaction product was dried at 40°C for 16 hours.

[0688] Based on the above, polymer P7 was obtained by using A-TMM-3LM-N and 4-HBA to open the ring of the maleic anhydride-derived structural unit in the raw material polymer and reacting it with GMA.

[0689] GPC measurements of polymer P7 confirmed the disappearance of peaks for the polyfunctional (meth)acrylic acid compounds, monofunctional (meth)acrylic acid compounds, and epoxy-containing (meth)acrylic acid compounds used. This confirmed that the obtained polymer P7 did not contain unreacted (meth)acrylic acid compounds, (meth)acrylic acid compounds without hydroxyl groups, or unreacted (meth)acrylic acid compounds containing epoxy groups.

[0690] Table 1 shows the components used in the synthesis example and the amount of each component, converted to maleic anhydride (MA), and by... 1 The amount (mole fraction, mol%) of each structural unit was calculated by H-NMR integral analysis and expressed in maleic anhydride (MA) conversion.

[0691] Furthermore, in the GPC measurements of the reaction solutions before and after the ring-opening reaction and before and after the GMA addition reaction, the peaks originating from the trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) decreased before and after the ring-opening reaction, and the peaks originating from GMA decreased before and after the GMA addition reaction. This also indicates that A-TMM-3LM-N and GMA were introduced into the polymer.

[0692] A polymer solution 23 containing polymer P7 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0693] [Comparative Example 2]

[0694] Except for changing the amount of 4-HBA added to 13.50 g, GMA to 13.31 g, and MEK to 100.80 g, polymer P8 was prepared in the same manner as in Comparative Example 1, and polymer solution 24 containing polymer P8 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0695] [Comparative Example 3]

[0696] (Polymer Synthesis)

[0697] Polymer P9 was prepared by ring-opening of the MA unit of raw polymer 2 using a monofunctional (meth)acrylic acid compound (HEMA), followed by reaction with an epoxy-containing (meth)acrylic acid compound (GMA). Details are described below.

[0698] First, a solution was prepared by adding 111.43 g of MEK to 60 g (0.312 mol MA equivalent) of the starting polymer 2. Next, 25.38 g (0.195 mol) of HEMA was added to the solution, followed by 6.00 g (0.059 mol) of triethylamine, and the reaction was carried out at 70°C for 6 hours. Subsequently, 13.31 g (0.094 mol) of GMA was added, and the reaction was carried out at 70°C for 4 hours to prepare the reaction solution.

[0699] The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. Subsequently, the polymer was purified by the following steps.

[0700] Use excess water to cause the polymer to reprecipitate.

[0701] The polymer powder obtained by washing with excess water and then re-precipitating was repeatedly subjected to the process twice.

[0702] The obtained reaction product was dried at 40°C for 16 hours.

[0703] Through the above, polymer P9 was obtained by using HEMA to open the ring of the maleic anhydride-derived structural units in the raw material polymer and reacting them with GMA.

[0704] GPC measurements of polymer P9 confirmed the disappearance of both the peaks of the monofunctional (meth)acrylic acid compound and the peaks of the epoxy-containing (meth)acrylic acid compound. This confirmed that the obtained polymer P9 contained neither unreacted (meth)acrylic acid compounds nor epoxy-containing (meth)acrylic acid compounds.

[0705] Table 1 shows the components used in the synthesis example and the amount of each component, converted to maleic anhydride (MA), and by... 1 The amount (mole fraction, mol%) of each structural unit was calculated by H-NMR integral analysis and expressed in maleic anhydride (MA) conversion.

[0706] By 1 H-NMR measurements confirmed that polymer P9 has a ring-opening structure with HEMA and a structure that has reacted with GMA.

[0707] A polymer solution 25 containing polymer P9 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0708] [Comparative Example 4]

[0709] (Polymer Synthesis)

[0710] Except that polymer 3 was used instead of polymer 1, a polymer solution 26 containing polymer P11 was prepared in the same manner as in Example 12. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0711] [Comparative Example 5]

[0712] (Polymer Synthesis)

[0713] Except that raw material polymer 12 was used instead of raw material polymer 1, polymer P22 was prepared in the same manner as in Example 3 by opening the MA unit of raw material polymer 12 with a trifunctional (meth)acrylic acid compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic acid compound (4-HBA), and then reacting it with an epoxy-containing (meth)acrylic acid compound (GMA) to obtain polymer P22.

[0714] A polymer solution 27 containing polymer P22 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared in the same manner as in Example 1.

[0715] <Evaluation Methods>

[0716] The polymers, polymer solutions, and photosensitive resin compositions synthesized in the Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 1-3.

[0717] (Weight-average molecular weight (Mw), molecular weight distribution (PDI))

[0718] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (PDI: Mw / Mn) used polystyrene conversion values ​​derived from calibration curves of standard polystyrene (PS) obtained by GPC measurements. Measurement conditions are as follows. The results are shown in Table 1.

[0719] The gel permeation chromatography system HLC-8320GPC is manufactured by Tosoh Corporation.

[0720] Tube column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation.

[0721] Detector: RI detector for liquid chromatography.

[0722] Temperature measured: 40℃.

[0723] Solvent: THF.

[0724] Sample concentration: 2.0 mg / mL.

[0725] (Developability evaluation (dissolution rate of the polymer (or photosensitive resin composition) to the alkaline developer))

[0726] The polymer solution (or photosensitive resin composition) obtained in the examples and comparative examples was spin-coated onto a wafer, and the PGMEA was dried and then pre-baked at 100°C for 2 minutes to produce a resin film with a thickness of 2 μm ± 0.2.

[0727] The resin film, along with the wafer, was immersed in a 2.38% by mass TMAH aqueous solution at 23°C, and the dissolution rate of the resin film was measured.

[0728] The dissolution rate was calculated by visually observing the impregnated wafer, measuring the time until the resin film dissolved and no interference pattern was visible, and dividing the film thickness by this time. The results are shown in Tables 1-3. For polymer solutions, a dissolution rate of 200 nm / s or more but less than 2000 nm / s is considered to indicate good developability. For photosensitive resin compositions, a dissolution rate of 200 nm / s or more but less than 2500 nm / s is considered to indicate good developability.

[0729] [Sensitivity evaluation of the photosensitive resin composition (2.38% by mass TMAH aqueous solution)]

[0730] (The residual film rate becomes over 90% of the exposure)

[0731] The photosensitive resin compositions obtained in the examples and comparative examples were spin-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 film A with a thickness of about 3.0 μm (±0.3 μm).

[0732] The thin film A was subjected to a photomask with a grayscale gradation of 1–100% opacity, and then aligned using a g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. at 100 mJ / cm². 2 The exposure amount was used for g+h+i ray exposure.

[0733] After exposure, the film was developed in a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for the development times specified in Tables 2 and 3 (immersed together with the wafer), thereby obtaining a film with a wavelength of 1–100 mJ / cm⁻¹. 2 Thin film B is exposed and developed at various exposure levels.

[0734] Based on the film thicknesses of films A and B obtained using the above method, the residual film rate can be calculated using the following formula.

[0735] Residual film yield (%) = (film thickness of film B at each exposure level / film thickness of film A) × 100

[0736] Then, the exposure amount at which the residual film rate is 90% or higher was used as the sensitivity of each photosensitive resin composition. The results are shown in Tables 2 and 3. An exposure amount of 50 mJ / cm² is required to achieve a residual film rate of 90% or higher. 2 The following are considered to be suitable for use as photosensitive compositions without any problems, if the concentration is 20 mJ / cm. 2 The following values ​​can be considered as having good sensitivity, such as 10 mJ / cm. 2 The following can be considered to have particularly excellent sensitivity.

[0737] [Yellow Index]

[0738] A photosensitive resin composition was spin-coated onto EAGLE XG glass (manufactured by Corning Incorporated Co., Ltd., 0.5 mm thick) and baked on a hot plate at 100°C for 120 seconds to obtain a film with a thickness of approximately 3.0 μm (±0.1 μm).

[0739] Next, the thin film was aligned using a g+h+i ray mask aligner (PLA-600F) manufactured by Canon Inc. at 100 mJ / cm². 2 The exposure amount was used for g+h+i ray exposure.

[0740] After exposure, the film was developed in a 2.38% (w / w) TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (immersed together with the wafer), thereby obtaining a film with a speed of 100 mJ / cm². 2 The film was exposed and developed based on the exposure amount.

[0741] The film was heated at 230°C in air for 30 minutes. After cooling the film to room temperature air, it was again heated at 230°C in air for 30 minutes. This process was repeated a total of three times, for a total of 30 minutes of heating in air.

[0742] Using a CR-5 colorimeter (manufactured by Konica Minolta, Inc.), the yellow index (YI) of the film obtained by the above method was measured three times by changing the measurement site, 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 Incorporated Co., Ltd., 0.5 mm thick). The results are shown in Tables 2 and 3. If the yellow index is 1.15 or below, it can be considered that it can be used as a photosensitive resin composition without any problems; if it is 1.10 or below, it can be considered that the heat-sensitive color change is good; if it is 0.8 or below, it can be considered that the heat-sensitive color change is particularly good.

[0743] [Seamless adhesion during development]

[0744] (Regarding the tightness of the line pattern)

[0745] A photosensitive resin composition was spin-coated onto EAGLE XG glass (manufactured by Corning Incorporated Co., Ltd., 0.5 mm thick) and baked on a hot plate at 100°C for 120 seconds to obtain a film with a thickness of approximately 3.0 μm (±0.1 μm).

[0746] For this thin film, a photomask having a total of five glass portions (exposure portions) alternating between glass portions (exposure portions) with a width of 40 μm and a height of 400 μm and chromium portions (shading portions) with a width of 40 μm and a height of 400 μm was used. A g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. was used at 18 mJ / cm². 2The photomask was exposed to g+h+i rays at a specified exposure level. Through this exposure, the glass portion of the photomask was exposed at the specified exposure level due to the transmitted light, while the chromium portion remained unexposed due to the absence of transmitted light, thus obtaining a line pattern alternating between exposed and unexposed areas. After exposure, the film was developed in a 0.5% (w / w) TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (immersed together with the wafer), thereby obtaining a wavelength of 18 mJ / cm². 2 The film was exposed and developed using the specified exposure amount. Five line patterns, each 40 μm wide and 400 μm wide, were examined under a microscope after exposure and development to determine if any peeling had occurred.

[0747] (Judgment Criteria)

[0748] ○: The developed line pattern is in close contact with the substrate, and no peeling areas were observed.

[0749] ×: In the developed line pattern, the area peeled off from the substrate is observed.

[0750] (Fitness of dot pattern)

[0751] A photosensitive resin composition was spin-coated onto EAGLE XG glass (manufactured by Corning Incorporated Co., Ltd., 0.5 mm thick) and baked on a hot plate at 100°C for 120 seconds to obtain a film with a thickness of approximately 3.0 μm (±0.1 μm).

[0752] For this thin film, a photomask with a pattern of three glass portions (exposure portions) each 50 μm wide and 50 μm wide and surrounded by chromium portions (shielding portions) was used. A g+h+i ray mask aligner (PLA-501F) manufactured by Canon Inc. was used at 18 mJ / cm². 2 The photomask was exposed to g+h+i rays at a specified exposure level. Through this exposure, the glass portion of the photomask was exposed at the specified exposure level due to the transmitted light, while the chromium portion remained unexposed due to the absence of transmitted light, thus obtaining a dot pattern with exposed portions of 50 μm wide and 50 μm wide. After exposure, the film was developed in a 0.5% (w / w) TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (immersed together with the wafer), thereby obtaining a wavelength of 18 mJ / cm². 2 The film was exposed and developed using the specified exposure amount. For the dot patterns at a total of 3 locations with a width of 50 μm and a length of 50 μm after exposure and development, the line patterns were observed under a microscope to check for peeling.

[0753] (Judgment Criteria)

[0754] ○: The dot pattern after development is in close contact with the substrate, and no peeling areas were observed.

[0755] ×: In the developed dot pattern, the area peeled off from the substrate is observed.

[0756]

[0757]

[0758] [Table 3]

[0759] Table 2

[0760]

[0761] [Table 4]

[0762] Table 3

[0763]

[0764] The polymers synthesized in Examples 1-6 and 12-22 all have the structure represented by general formula (P), and can produce resin cured products with good sensitivity, reduced yellowing, excellent transparency, and excellent adhesion to substrates, etc. Furthermore, the polymers synthesized in Examples 1-6 and 12-19, in which the thiol-containing compound introduced into the polymer is a thiol-containing compound with three or more functions and containing an ester structure, exhibit particularly reduced yellowing and excellent transparency. On the other hand, the polymers synthesized in Comparative Examples 1-4 without using a thiol-containing compound and in Comparative Example 5 using a monofunctional thiol-containing compound resulted in resin cured products with low transparency and therefore low adhesion to substrates, etc.

[0765] The polymer solutions of Examples 7 to 11, in which a specified coupling agent (a compound having a thiol group and an alkoxy group) was further added to the polymer solutions of Examples 1 to 5, exhibited even better sensitivity and reduced yellowing, resulting in even better adhesion to the substrate.

[0766] <Making a Color Filter>

[0767] A colored photosensitive resin composition was prepared by further adding an appropriate amount of pigment dispersion NX-061 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., green) to the photosensitive resin compositions prepared in Examples 1 to 22.

[0768] By forming a film on a substrate and then subjecting it to exposure, alkaline development, and other processes, a green color filter can be formed.

[0769] Furthermore, as a pigment dispersion, it can replace NX-061 and be used with the company's NX-053 (blue), NX-032 (red), etc., to form blue or red color filters.

[0770] <The Creation of the Black Matrix>

[0771] A black photosensitive resin composition was prepared by further adding an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) to the photosensitive resin compositions prepared in Examples 1 to 22.

[0772] A black matrix can be formed by depositing a film on a substrate and then subjecting it to exposure, alkaline development, and other processes.

[0773] This application claims priority based on Japanese Application No. 2020-158807 filed on September 23, 2020 and Japanese Application No. 2020-201731 filed on December 4, 2020, and incorporates in its entirety the disclosures herein.

[0774] Explanation of reference numerals in the attached figures

[0775] 10: Substrate; 11: Black matrix; 12: Color filter; 13: Protective film; 14: Transparent electrode layer.

Claims

1. A polymer, wherein, The polymer is represented by the following general formula (P), In the general formula (P), Y is an organogroup with 1 to 30 carbon atoms in a 1 to 6 valence derived from compounds represented by the following chemical formulas (s-1) to (s-21). Chain contains structural units represented by the following general formula (AE-1) and structural units represented by the following general formula (AE-2). In general formula (AE-1), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or an alkyl group with 1 to 6 substituted or unsubstituted carbon atoms, and X represents an oxygen atom or an alkylene group with 1 to 4 substituted or unsubstituted carbon atoms. The alkyl group of Q is bonded to any carbon atom of the alkylene group of X to form a ring or is not bonded. In general formula (AE-2), R... A The group contains one or more (meth)acryloyl groups, wherein the substituents of the substituted alkyl group having 1 to 6 carbon atoms and the substituents of the substituted alkylene group having 1 to 4 carbon atoms are halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, or mercapto groups. n is an integer from 1 to 6, and Y has a structure other than Chain, whether it is bonded or not.

2. The polymer according to claim 1, wherein, Y is an organic group with 1 to 30 carbon atoms in a 1 to 6 valence derived from a thiol-containing compound with 3 or more functions selected from the compounds represented by the chemical formulas (s-1) to (s-21).

3. The polymer according to claim 1 or 2, wherein, Y is an organic group with 1 to 30 carbon atoms in a 1 to 6 valence derived from compounds containing an ester structure selected from compounds represented by the chemical formulas (s-1) to (s-21).

4. The polymer according to claim 1 or 2, wherein, The Chain also contains structural units represented by the following general formula (NB). In the general formula (NB), R 1 R 2 R 3 and R 4 Each is an organic group consisting of 1 to 30 hydrogen or carbon atoms, where a1 is 0, 1, or 2. The organic groups having 1 to 30 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, allyl, pentenyl, vinyl, ethynyl, methylene, ethylene, tolyl, xylyl, phenyl, naphthyl, anthracene, benzyl, phenethyl, adamantyl, cyclopentyl, cyclohexyl, cyclooctyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, epoxy, or oxacyclobutyl, which may be substituted with or unsubstituted by fluorine atoms, hydroxyl groups, or carboxyl groups.

5. The polymer according to claim 1 or 2, wherein, The Z contains a group represented by the following general formula (1a), In general formula (1a), R is a hydrogen atom, methyl or ethyl.

6. The polymer according to claim 1 or 2, wherein, The chain contains structural units represented by the following general formula (D). In general formula (D), R D It is a group containing a polyfunctional (meth)acryloyl group.

7. The polymer according to claim 1 or 2, wherein, The R A It contains at least one group containing 2 to 6 (meth)acryloyl groups.

8. The polymer according to claim 1 or 2, wherein, The R A Contains at least one group represented by the following general formula (1b), (1c) or (1d), In general formula (1b), k is 2 or 3 R can be a hydrogen atom or a methyl group; multiple Rs may be the same or different. X 1 It is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX-, with multiple X's. 1 Whether they are the same or different, in -ZX-, Z is -O- or -OCO-, and X is an alkylene group with 1 to 6 carbon atoms. X 1 The ' is 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 It is an organic group with a valence of k+1 and a carbon number of 1 to 12. In general formula (1c), k, R, X 1 and X 2 respectively with R, k, and X in the above general formula (1b) 1 and X 2 The same meaning, multiple Rs are the same or different from each other, multiple Xs 1 Whether they are the same or different, X 3 It is a divalent organic group with 1 to 6 carbon atoms. X 4 and X 5 They are either independent single bonds or divalent organic groups with 1 to 6 carbon atoms. X 6 It is a divalent organic group with 1 to 6 carbon atoms. In the general formula (1d), n is an integer from 2 to 5.

9. The polymer according to claim 1 or 2, wherein, The chain contains structural units represented by the following general formula (S). In the general formula (S), R S It is a group containing only one (meth)acryloyl group.

10. The polymer according to claim 1 or 2, wherein, The chain also contains structural units represented by the following general formula (MA). 。 11. The polymer according to claim 1 or 2, wherein, The Chain also contains at least one structural unit selected from the structural units represented by the following general formula (E) and the following general formula (EE). In general formulas (E) and (EE), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, substituted or unsubstituted, and X represents an oxygen atom or an alkylene group with 1 to 4 carbon atoms, substituted or unsubstituted, wherein the alkyl group of Q is bonded to any carbon atom of the alkylene group of X to form a ring or is unbonded, and the substituents of the substituted alkyl group with 1 to 6 carbon atoms and the substituents of the substituted alkylene group with 1 to 4 carbon atoms are halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, or mercapto groups. In the general formula (EE), there are multiple Z, Q and X that are the same or different.

12. The polymer according to claim 1 or 2, wherein, The chain also contains structural units represented by the following general formula (M). 。 13. The polymer according to claim 1, wherein, The polymer is represented by the following general formula (P1), In the general formula (P1), p, q, and r represent the molar contents of A, B, and C in the polymer, respectively, p + q + r = 1, p is greater than 0, q is greater than 0, and r is greater than 0. p, q, or r may be the same or different in each of the n structural units within the [ ]. n is an integer from 1 to 6. X is a hydrogen or an organic group with 1 or more carbon atoms but less than 30. The organic groups having 1 to 30 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, allyl, pentenyl, vinyl, ethynyl, methylene, ethylene, tolyl, xylyl, phenyl, naphthyl, anthracene, benzyl, phenethyl, adamantyl, cyclopentyl, cyclohexyl, cyclooctyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, epoxy, or oxacyclobutyl, which may be substituted with or unsubstituted by fluorine, hydroxyl, or carboxyl groups. Y is an organogroup with 1 to 30 carbon atoms in a 1 to 6 valence derived from compounds represented by the following chemical formulas (s-1) to (s-21). A contains structural units represented by the following general formula (NB). B contains structural units represented by the following general formula (AE). C contains divalent structural units derived from copolymeric compounds with double bonds. The copolymers containing double bonds are indene, maleimide, styrene, acenaphthene, norbornene, dihydrofuran, pinene, limonene, pentene, cyclohexene, cyclododecanetriene, tricycloundecene, dimethyl fumarate, ethyl fumarate, dibutyl fumarate, coumarin, methyl methacrylate, methyl acrylate, vinyl acetate, or 2-hydroxyethyl vinyl ether, wherein these groups are substituted with alkyl or aryl groups or are unsubstituted. There exist multiple A's, B's, or C's that are the same as or different from each other. Y may have other structures besides the polymer chain represented by [ ]n, whether bonded or unbonded. In the general formula (NB), R 1 R 2 R 3 and R 4 Each is an organic group consisting of 1 to 30 hydrogen or carbon atoms, where a1 is 0, 1, or 2. The organic groups having 1 to 30 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, allyl, pentenyl, vinyl, ethynyl, methylene, ethylene, tolyl, xylyl, phenyl, naphthyl, anthracene, benzyl, phenethyl, adamantyl, cyclopentyl, cyclohexyl, cyclooctyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, epoxy, or oxacyclobutyl, which may be substituted with or unsubstituted by fluorine, hydroxyl, or carboxyl groups. In the general formula (AE), Z, Q, and X have the same meaning as in the general formula (AE-1), and R... A It is a group containing one or more (meth)acryloyl groups.

14. The polymer according to claim 13, wherein, The divalent structural units constituting C are the divalent structural units represented by the following general formulas (1) to (4). In the general formula (1), R 1 and R 2 Each of the following can independently represent a hydrogen atom, an alkyl group, or an aryl group; in the general formula (2), R 3 Represents a hydrogen atom, alkyl group, or aryl group; in the general formula (3), R 4 ~R 6 Each of the following can independently represent a hydrogen atom, an alkyl group, or an aryl group; in the general formula (4), R 7 ~R 10 Each can be an organic group that independently represents a hydrogen atom, a hydroxyl group, or an organic group with 1 to 30 carbon atoms.

15. The polymer according to claim 13 or 14, wherein, The B contains at least one structural unit selected from the structural units represented by the following general formulas (DE) and (SE), and may contain, as needed, at least one structural unit selected from the structural units represented by the following general formulas (D), (S), (MA), (E), (EE), and (M). In the general formula (DE), Q, X, and Z have the same meaning as in the general formula (AE-1), and R... D It is a group containing two or more (meth)acryloyl groups. In the general formula (SE), Q, X, and Z have the same meaning as in the general formula (AE-1), and R S It is a group containing only one (meth)acryloyl group. In general formula (D), R D It is a group containing a polyfunctional (meth)acryloyl group. In the general formula (S), R S It is a group containing only one (meth)acryloyl group. In general formula (E), Z, Q, and X have the same meaning as in general formula (AE-1). In the general formula (EE), Z, Q, and X have the same meaning as in the general formula (AE-1). There may be multiple instances where Z, Q, and X are the same or different. 。 16. The polymer according to claim 1 or 13, wherein, The organogroup constituting Y contains an organogroup with 1 to 30 carbon atoms in a 1 to 6 valence derived from at least one compound selected from compounds represented by the following chemical formulas (s-1) to (s-3), (s-5), and (s-8) to (s-10). 。 17. A polymer, wherein, The polymer is obtained through the following process: A raw material polymer is prepared by polymerizing a monomer composition containing a monomer represented by the following general formula (NBm) and maleic anhydride in the presence of a difunctional or higher thiol-containing compound. The obtained raw material polymer is reacted with polyfunctional (meth)acrylic acid monomers and / or monofunctional (meth)acrylic acid monomers in the presence of an alkaline catalyst to prepare a polymer precursor; and Next, the obtained polymer precursor is reacted with an epoxy-containing (meth)acrylic acid compound in the presence of a catalyst to obtain the polymer. In the general formula (NBm), R 1 R 2 R 3 and R 4 Each is an organic group consisting of 1 to 30 hydrogen or carbon atoms, where a1 is 0, 1, or 2. The organic groups having 1 to 30 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, allyl, pentenyl, vinyl, ethynyl, methylene, ethylene, tolyl, xylyl, phenyl, naphthyl, anthracene, benzyl, phenethyl, adamantyl, cyclopentyl, cyclohexyl, cyclooctyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, epoxy, or oxacyclobutyl, which may be substituted with or unsubstituted by fluorine atoms, hydroxyl groups, or carboxyl groups.

18. The polymer according to claim 17, wherein, In the raw material polymer, polymer chains having structural units represented by the following general formula (NB) and the following general formula (MA) are bonded via thioether groups derived from at least one thiol group of the thiol-containing compound with two or more functions. In the general formula (NB), R 1 R 2 R 3 and R 4 a1 has the same meaning as the general formula (NBm). 。 19. The polymer according to claim 18, wherein, In the polymer precursor, polymer chains having structural units represented by the general formula (NB), structural units represented by the following general formula (D), and / or structural units represented by the following general formula (S) are bonded via thioether groups derived from at least one thiol group of the thiol-containing compound with two or more functions. In general formula (D), R D For groups containing two or more (meth)acryloyl groups, in the general formula (S), R S It is a group containing only one (meth)acryloyl group.

20. The polymer according to claim 19, wherein, In the polymer, polymer chains having structural units represented by the general formula (NB), the general formula (D), and / or the general formula (S), the general formula (DE), and / or the general formula (SE) are bonded via thioether groups derived from at least one thiol group of the thiol-containing compound with two or more functions. In the general formula (DE), Z is a group containing one or more (meth)acryloyl groups, Q is a hydrogen atom or an alkyl group with 1 to 6 substituted or unsubstituted carbon atoms, X represents an oxygen atom or an alkylene group with 1 to 4 substituted or unsubstituted carbon atoms, wherein the alkyl group of Q is bonded to any carbon atom of the alkylene group of X to form a ring or is unbonded, and R D It is a group containing two or more (meth)acryloyl groups. The substituents of the substituted alkyl group having 1 to 6 carbon atoms and the substituents of the substituted alkylene group having 1 to 4 carbon atoms are halogen atoms, hydroxyl groups, carboxyl groups, amino groups, cyano groups, or mercapto groups. In the general formula (SE), Z, Q, and X have the same meaning as in the general formula (DE), and R... S It is a group containing only one (meth)acryloyl group.

21. The polymer according to claim 17 or 18, wherein, Before reacting the polymer precursor with the epoxy-containing (meth)acrylic acid compound, water is added to the polymer precursor and the mixture is heated in the presence of a catalyst.

22. The polymer according to claim 17 or 18, wherein, The polymer is obtained by reacting the polymer precursor with the epoxy-containing (meth)acrylic acid compound, followed by adding water to the reactants and heating.

23. A polymer solution, wherein, The polymer solution contains the polymer according to any one of claims 1 to 22.

24. The polymer solution according to claim 23, wherein, The polymer solution also contains compounds having thiol and alkoxy groups or oligomers thereof.

25. The polymer solution according to claim 24, wherein, The compound having a thiol group and an alkoxy group has a structure in which a thiol group and an alkoxy group are bonded to an organic chain containing or not containing one or more atoms selected from O, N, S, P and Si.

26. The polymer solution according to claim 24, wherein, The compounds having a thiol group and an alkoxy group contain compounds represented by the following general formula (a). In general formula (a), R independently represents an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and at least two Rs are alkoxy groups having 1 to 3 carbon atoms. L represents an m+n valence organic chain that may or may not contain one or more atoms selected from O, N, S, P, and Si. X represents a single bond or a divalent organic group, which may or may not contain a carbonyl group, ester group, thioester group, amide group, or thioamide group. Q represents a single bond or a divalent organic group, with or without a carbonyl, ester, thioester, amide, or thioamide group. The m:n ratio is 1:1 to 1:8, and the weight-average molecular weight of the compound is 100 to 2000. Here, m:n is a molar ratio.

27. The polymer solution according to any one of claims 23 to 26, wherein, The polymer solution is used to form a color filter or a black matrix.

28. A photosensitive resin composition, wherein, The photosensitive resin composition comprises: The polymer solution according to any one of claims 23 to 27; Multifunctional (meth)acrylate monomers; and Photopolymerization initiator.

29. A solidified material, wherein, The cured product is a cured product of the photosensitive resin composition according to claim 28.

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