KR20230071160A - Polymers, polymer solutions and photosensitive resin compositions - Google Patents

Abstract

(일반식 (P) 중, Y는, 2관능 이상의 싸이올기 함유 화합물로부터 유도되는 1~6가의 탄소수 1 이상 30 이하의 유기기이며, Chain은, 하기 일반식 (AE-1)로 나타나는 구조 단위 및 하기 일반식 (AE-2)로 나타나는 구조 단위를 포함하고, n은 1~6의 정수이다.)

The polymer of the present invention is represented by the following general formula (P).

(In the general formula (P), Y is a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a compound containing a bifunctional or higher thiol group, and Chain is a structural unit represented by the following general formula (AE-1) And a structural unit represented by the following general formula (AE-2), where n is an integer of 1 to 6.)

Description

Polymers, polymer solutions and photosensitive resin compositions

The present invention relates to polymers, polymer solutions and photosensitive resin compositions.

A liquid crystal display device or a solid-state imaging device usually includes a color filter or a black matrix. For formation of a color filter or a black matrix, a photosensitive resin composition is often used.

For example, in claim 1 of patent document 1, a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator having a group having an acidic group and two or more types of mutually different polymerizable unsaturated groups in at least a side chain. are listed. Moreover, in the Example of Patent Document 1, it is described that methacrylic acid/allyl methacrylate/glycidyl adduct was synthesized as an alkali-soluble resin, and a photosensitive resin composition was prepared using this.

Patent Document 2 discloses a resin composition containing a resin containing an epoxy group and an acid group, a polybasic acid monoester of a hydroxyl group-containing polyfunctional (meth)acrylate, and a solvent, with respect to 1 mole of the acid group in the resin containing an epoxy group and an acid group. , A resin composition characterized in that the epoxy group is 0.5 to 3.0 mol is described.

Patent Literature 3 discloses a method for producing a polymer including a step of reacting a compound having an epoxy group with a precursor polymer having a maleic anhydride moiety ring-opened. As a compound having an epoxy group, glycidyl methacrylate is described.

Patent Document 1: International Publication No. 2012/147706 Patent Document 2: International Publication No. 2016/103844 Patent Document 3: International Publication No. 2017/154439

For the photosensitive resin composition for forming a color filter or a black matrix, a polymer having a property of being cured by light-induced polymerization is used. A color filter and a black matrix are produced by hardening this, after patterning the photosensitive resin composition by exposure and image development.

In the photosensitive resin composition, "high sensitivity" is also considered as a general subject, but with the complexity and spread of display devices and imaging devices, higher level of sensitivity is required. The higher the sensitivity of the photosensitive resin composition (the higher the sensitivity), the shorter the time required for exposure, and the higher the productivity.

Moreover, it is necessary for the hardened|cured material of the photosensitive resin composition to suppress yellowing and to be excellent in transparency and heat discoloration resistance. Further, when a pattern is formed by applying the photosensitive resin composition to a substrate or the like, exposing and developing the obtained coating film, it is required to have excellent adhesion to the substrate or the like from the viewpoint of product yield and product reliability.

In Patent Literatures 1 to 3, there was room for improvement in these characteristics.

The inventors of the present invention have found that a cured resin product having good sensitivity, suppressed yellowing, high heat discoloration resistance, and excellent adhesion to a substrate can be obtained by improving the polymer used in the photosensitive resin composition, and reached the present invention. .

That is, this invention can be shown below.

According to the present invention,

A polymer represented by the following general formula (P) can be provided.

[Formula 1]

(In the general formula (P),

Y is a monovalent to hexavalent organic group of 1 to 30 carbon atoms derived from a bifunctional or higher thiol group-containing compound;

Chain includes a structural unit represented by the following general formula (AE-1) and a structural unit represented by the following general formula (AE-2).)

[Formula 2]

(In formula (AE-1), Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X is an oxygen atom or a substituted Alternatively, it represents an unsubstituted alkylene group having 1 to 4 carbon atoms, and a ring may be formed by bonding the carbon atom of any one of the alkylene group of Q and the alkylene group of X. In general formula (AE-2), R ^A is , It is a group containing one or more (meth)acryloyl groups.

n is an integer of 1-6. A structure other than Chain may be combined with Y.)

According to the present invention,

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 bifunctional or higher thiol group-containing compound,

A polymer precursor is prepared by reacting the obtained raw material polymer with a polyfunctional (meth)acrylic monomer and/or a monofunctional (meth)acrylic monomer in the presence of a basic catalyst,

Subsequently, a polymer obtained by reacting the obtained polymer precursor with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst can be provided.

[Formula 3]

(In general formula (NBm), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2.)

According to the present invention, a polymer solution containing the polymer can be provided.

According to the present invention,

A photosensitive resin composition comprising the polymer solution, a polyfunctional (meth)acrylate monomer, and a photopolymerization initiator may be provided.

According to the present invention,

A cured product of the photosensitive resin composition may be provided.

According to the polymer of the present invention, it is possible to provide a cured resin product having good sensitivity, reduced yellowing, excellent transparency, and excellent adhesion to a substrate or the like. In other words, the polymer of the present invention can provide a cured resin product with excellent balance of these properties.

1 is a diagram (cross-sectional view) schematically showing an example of a structure of a liquid crystal display device and/or a solid-state imaging device.
2 is a ¹ H-NMR chart of polymer P1 obtained in Example 1.
FIG. 3 is an enlarged view of a peak around 6.0 ppm in ^{the 1} H-NMR chart of FIG. 2 .

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described, referring drawings. In addition, in all drawings, the same code|symbol is attached|subjected to the same component, and description is abbreviate|omitted suitably. In addition, all drawings are for explanatory purposes only. The shape, size ratio, etc. of each member in the drawings do not necessarily correspond to actual articles. In this specification, notation "a to b" in the description of a numerical range indicates a or more and less than b unless otherwise specified. For example, "5 to 90%" means "5% or more and 90% or less".

In the notation of a group (atomic group) in this specification, the notation that does not describe whether it is substituted or unsubstituted includes both those without a substituent and those with a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The notation "(meth)acryl" in this specification shows the concept containing both an acryl and methacryl. The same applies to similar notations such as "(meth)acrylate".

In particular, the "(meth)acryloyl group" in the present specification refers to an acryloyl group represented by -C(=O)-CH=CH ₂ and -C(=O)-C(CH ₃ )=CH ₂ Represents a concept including a methacryloyl group represented by.

[Polymer (A)]

The polymer (A) of the present embodiment has a structure in which at least one polymer chain represented by the following Chain is bonded to a mono- or hexavalent organic group having 1 to 6 valent carbon atoms and 30 or less carbon atoms derived from a bifunctional or higher thiol group-containing compound.

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

[Formula 4]

In general formula (P), Chain contains the structural unit represented by the following general formula (AE-1) and the structural unit represented by the following general formula (AE-2). Polymer P containing these structural units can provide a cured resin product having good sensitivity, excellent alkali solubility, reduced yellowing and excellent transparency, and excellent adhesion to substrates and the like. In other words, the polymer of the present invention is excellent in the balance of these properties.

[Formula 5]

In general formula (AE-1), Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X represents an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and the alkyl group of Q and the carbon atom of any one of the alkylene groups of X may bond to form a ring.

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

n is an integer of 1-6.

Since the polymer (A) of the present embodiment has a structure represented by the general formula (P), a cured resin product having good sensitivity, reduced yellowing, excellent transparency, and excellent adhesion to a substrate or the like can be obtained. can provide

In general formula (AE-1), Z is not particularly limited as long as it is a group containing one or more (meth)acryloyl groups, but more preferably a group containing 1 to 4 (meth)acryloyl groups, ( It is more preferable that it is a group containing 1-3 meth)acryloyl groups. By optimizing the number of (meth)acryloyl groups included in Z, the sensitivity is excellent and the alkali solubility (developability) is excellent, in other words, these balance is excellent.

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

[Formula 6]

In general formula (1a), R is a hydrogen atom, a methyl group, or an ethyl group.

In general formula (AE-1), Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. As a substituent of the substituted C1-C6 alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group, etc. are mentioned.

In general formula (AE-1), X is an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms.

As an alkylene group, a methylene group, an ethylene group, a propylene group, and a butylene group are mentioned. As a substituent of the substituted C1-C4 alkylene group, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a mercapto group, etc. are mentioned.

In the general formula (AE-1), the alkyl group of Q and the carbon atom of any one of the alkylene groups of X may bond to form a ring. As a ring structure, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a decalin ring, a benzene ring, a naphthalene ring, etc. are mentioned.

In general formula (AE-2), R ^A is not particularly limited as long as it is a group containing one or more (meth)acryloyl groups, but is preferably a group containing 1 to 6 (meth)acryloyl groups, ( It is more preferably a group containing 1 to 5 meth)acryloyl groups, and more preferably a group containing 2 to 5 (meth)acryloyl groups. The sensitivity can be further increased by optimizing the number of (meth)acryloyl groups included in R ^A . Moreover, it becomes easy to make sensitivity and developability highly compatible. Moreover, it becomes easy to raise heat resistance more.

The ratio of the structural unit represented by the general formula (AE-1) in all the structural units included in the chain of the polymer (A) of the present embodiment is preferably 0.5 to 20 mol%, more preferably 1 to 15 mol. %am. The ratio of the structural unit represented by the general formula (AE-2) is preferably 6 to 40 mol%, more preferably 12 to 30 mol%.

As a structural unit represented by general formula (AE-2), the structural unit represented by the following general formula (AE-2a) and the structural unit represented by the following general formula (AE-2b) are mentioned, for example.

[Formula 7]

In general formula (AE-2a), R ^S is a group containing only one (meth)acryloyl group. In particular, in the design of a conventional photosensitive resin composition, when curing property is increased in order to increase sensitivity, curing progresses excessively and developability tends to be deteriorated. On the other hand, when developing property is improved, curing tends to be insufficient. For this reason, it is preferable that the chain of polymer (A) contains the structural unit represented by general formula (AE-2a), and this makes it compatible with both sensitivity and developability with a good balance.

R ^S is a group represented by the following general formula (Sa), for example.

[Formula 8]

In the general formula (Sa), X ¹⁰ is a divalent organic group, and R is a hydrogen atom or a methyl group.

The total carbon number of X ¹⁰ is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10.

In the general formula (Sa), X ¹⁰ is a divalent organic group, and R is a hydrogen atom or a methyl group.

The total carbon number of X ¹⁰ is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10.

As the divalent organic group for X ¹⁰ , for example, an alkylene group is preferable. Part of -CH ₂ - in this alkylene group may be an ether group (-O-). The alkylene group may be linear or branched, but is more preferably linear.

The divalent organic group of X ¹⁰ is more preferably a straight-chain alkylene group having 3 to 6 carbon atoms in total. By appropriately selecting the carbon number of X ¹⁰ (chain length of X ¹⁰ ), the structural unit represented by the general formula (AE-2a) becomes more likely to be involved in the crosslinking reaction, and the sensitivity can be increased.

The divalent organic group (eg, alkylene group) of X ¹⁰ may be substituted with an arbitrary substituent. As a substituent, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, etc. are mentioned.

In addition, the divalent organic group of X ¹⁰ may be an arbitrary group other than an alkylene group. For example, it may be a divalent group formed by linking one or two or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group, and the like.

The ratio of the structural unit represented by the general formula (AE-2a) in all the structural units included in the Chain of the polymer (A) of the present embodiment is preferably 5 to 40 mol%, more preferably 10 to 30 mol %am.

In the general formula (AE-2b), R ^D is not particularly limited as long as it is a group containing two or more (meth)acryloyl groups, but is more preferably a group containing 2 to 6 (meth)acryloyl groups, It is more preferable that it is a group containing 3-5 (meth)acryloyl groups. The sensitivity can be further increased by optimizing the number of (meth)acryloyl groups included in R ^D . Moreover, it becomes easy to make sensitivity and developability highly compatible. Moreover, it becomes easy to raise heat resistance more.

In addition, from the point of further improvement of sensitivity, it is preferable that R ^D contains two or more acryloyl groups (a group represented by -C(=O)-CH=CH ₂ ) from points such as steric hindrance.

R ^D is preferably a group represented by the following general formula (1b), (1c) or (1d). By being such a group, it tends to be easy to obtain the above various effects.

[Formula 9]

In the general formula (1b),

k is 2 or 3;

R is a hydrogen atom or a methyl group, and a plurality of R's may be the same or different,

X ¹ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z is -O- or -OCO-, X is an alkylene group having 1 to 6 carbon atoms), and a plurality of X ¹ may be the same or different,

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

X ² is a k+1 valent organic group having 1 to 12 carbon atoms.

R is preferably a hydrogen atom from the viewpoint of further improvement in sensitivity (easiness of polymerization) and the like.

Although k may be 2 or 3, it is preferably 3 from the viewpoint of ease of availability of raw materials and further improvement in sensitivity.

When X ¹ is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched.

When X ¹ is an alkylene group having 1 to 6 carbon atoms, X ¹ is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, still more preferably —CH ₂ —(methylene is).

When X ¹ is a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group of 1 to 6 carbon atoms in X may be linear. It may be branched.

The C1-C6 alkylene group of X is preferably a straight-chain alkylene group, more preferably a C1-C3 straight-chain alkylene group, still more preferably -CH ₂ -CH ₂ - (ethylene group) or -CH ₂ -CH(CH ₃ )-.

When X ¹ ' is an alkylene group having 1 to 6 carbon atoms, the specific aspect is the same as that of X ¹ .

When X ¹ ' is a group represented by -X'-Z'-, the specific aspect of X' is the same as the above X.

As the organic group having 1 to 12 carbon atoms and having a valent k+1 of X ² , an arbitrary group obtained by removing k+1 hydrogen atoms from any organic compound is exemplified. The "optional organic compound" herein is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less.

X ² is, for example, a group obtained by removing k+1 hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group obtained by removing k+1 hydrogen atoms from a straight chain hydrocarbon having 1 to 3 carbon atoms. In addition, the hydrocarbon here may also contain an oxygen atom (for example, an ether bond, a hydroxyl group, etc.). Moreover, it is preferable that a hydrocarbon is a saturated hydrocarbon.

As another aspect, X ² may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure and a group containing a heterocyclic structure (eg, isocyanuric acid structure).

[Formula 10]

In formula (1c),

k, R, X ¹ and X ² respectively have the same meaning as R, k, X ¹ and X ² in the above general formula (1b), and a plurality of Rs may be the same or different from each other, and a plurality of X ¹ of may be the same as or different from each other,

X ³ is a divalent organic group having 1 to 6 carbon atoms;

X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms;

X ⁶ is a divalent organic group having 1 to 6 carbon atoms.

Specific aspects, preferred aspects, etc. of R, k, X ¹ and X ² are the same as those described in General Formula (1b).

Examples of the divalent organic group of X ³ and X ⁶ of 1 to 6 carbon atoms include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. In addition, the hydrocarbon here may also contain an oxygen atom (for example, an ether bond, a hydroxyl group, etc.). Moreover, it is preferable that a hydrocarbon is a saturated hydrocarbon.

Examples of the divalent organic group of X ⁴ and X ⁵ having 1 to 6 carbon atoms include a linear or branched alkylene group. The carbon number of the linear or branched alkylene group is preferably 1 to 3.

[Formula 11]

In general formula (1d), n is an integer of 2-5, Preferably it is 2 or 3.

The ratio of the structural unit represented by the general formula (AE-2b) in all the structural units included in the chain of the polymer (A) of the present embodiment is preferably 1 to 30 mol%, more preferably 2 to 20 mol%. %am.

Chain of the polymer (A) of the present embodiment may contain a structural unit represented by the following general formula (AE) consisting of a structural unit represented by general formula (AE-1) and a structural unit represented by general formula (AE-2). can

[Formula 12]

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

The ratio of the structural unit represented by the general formula (AE) in all the structural units included in the chain of the polymer (A) of the present embodiment is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%. .

The Chain of the polymer (A) of the present embodiment may contain a structural unit represented by the following general formula (DE) consisting of a structural unit represented by the general formula (AE-1) and a structural unit represented by the general formula (AE-2b). can The polymer (A) containing a structural unit represented by the following general formula (DE) in the chain has good sensitivity, excellent alkali solubility, further reduced yellowing and excellent transparency, and better adhesion to substrates and the like. An excellent cured resin product can be provided. In other words, the polymer of the present invention is more excellent in the balance of these properties, and particularly excellent in sensitivity.

[Formula 13]

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

The ratio of the structural unit represented by the general formula (DE) in all the structural units included in the chain of the polymer (A) of the present embodiment is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%. .

Chain of the polymer (A) of the present embodiment is a structural unit composed of a structural unit represented by general formula (AE-1) and a structural unit represented by general formula (AE-2a), and has a structure represented by the following general formula (SE) units may be included.

[Formula 14]

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

When the polymer (A) contains the structural unit represented by the general formula (SE), the ratio of the structural unit represented by the general formula (SE) in all the structural units contained in the Chain of the polymer (A) is preferably 3. It is -35 mol%, More preferably, it is 7-25 mol%.

Chain of the polymer (A) of the present embodiment may further include a structural unit represented by the following general formula (NB).

[Formula 15]

In general formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2.

The structural unit represented by the general formula (NB) is chemically robust. Therefore, the polymer (A) containing this as a structural unit has a small weight loss and is stable when subjected to heat treatment. Therefore, the photosensitive resin composition containing the polymer (A) can be suitably used for producing a film or filter for use in a liquid crystal display device or a solid-state imaging device requiring heat resistance.

Examples of the organic group having 1 to 30 carbon atoms that can constitute R ¹ to R ⁴ include substituted or unsubstituted, linear or branched alkyl groups having 1 to 30 carbon atoms, and more specifically, an alkyl group and an alkenyl group. , an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, an alkoxy group, a heterocyclic group, a carboxyl group, and the like.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, and heptyl group. , an octyl group, a nonyl group, a decyl group, and the like.

As an alkenyl group, an allyl group, a pentenyl group, a vinyl group etc. are mentioned, for example.

As an alkynyl group, ethynyl group etc. are mentioned, for example.

As an alkylidene group, a methylidene group, an ethylidene group, etc. are mentioned, for example.

As an aryl group, a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and anthracenyl group are mentioned, for example.

As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned, for example.

As an alkaryl group, a tolyl group, a xylyl group, etc. are mentioned, for example.

As a cycloalkyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, A neopentyloxy group, n-hexyloxy group, etc. are mentioned.

As a heterocyclic group, an epoxy group, an oxetanyl group, etc. are mentioned, for example.

As R ¹ , R ² , R ³ and R ⁴ in the structural unit represented by general formula (NB), hydrogen or an alkyl group is preferable, and hydrogen is more preferable.

In addition, the hydrogen atom in the C1-C30 organic group of ^R1 , ^R2 , ^R3 and ^R4 may be substituted by arbitrary atomic groups. For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group or the like. More specifically, as the organic group having 1 to 30 carbon atoms for R ¹ , R ² , R ³ and R ⁴ , an alkyl fluoride group or the like may be selected.

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

The ratio of the structural unit represented by the general formula (NB) in all the structural units included in the chain of the polymer (A) is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, still more preferably It is 40-60 mol%.

Chain of the polymer (A) of the present embodiment may further include a structural unit represented by the following general formula (D) and/or a structural unit represented by the following general formula (S) from the viewpoint of the effect of the present invention.

[Formula 16]

In general formula (D), R ^D has the same meaning as in general formula (AE-2b).

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

[Formula 17]

In general formula (S), R ^S has the same meaning as in general formula (AE-2a).

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

In this embodiment, the polymer (A) may also contain a structural unit represented by the general formula (MA) in addition to the above structural units. The structural unit represented by the general formula (MA) is ring-opened by an alkaline developer, and generates two carboxyl groups as represented by the general formula (M) described later. Therefore, the polymer (A) containing the structural unit has excellent developability. When the chain of the polymer (A) includes the structural unit represented by the general formula (MA), the structural unit represented by the general formula (MA) among all the structural units included in the chain of the polymer (A) is preferably , 1 to 30 mol%, more preferably 2 to 25 mol%.

[Formula 18]

In addition, the content (ratio) of each structural unit contained in the chain of the polymer (A) is the input amount (molar amount) of the raw material used when synthesizing the chain of the polymer (A), the amount of the raw material remaining after synthesis, and various spectra ( For example, IR spectrum, ¹ H-NMR spectrum, ¹³ C-NMR spectrum) can be estimated/calculated from the presence of peaks, peak areas, and the like.

Chain of the polymer (A) of the present embodiment may further include a structural unit represented by the following general formula (E) and/or a structural unit represented by the following general formula (EE) from the viewpoint of the effect of the present invention.

[Formula 19]

In general formulas (E) and (EE), Z, Q, and X have the same meaning as in general formula (AE-1). In the general formula (EE), a plurality of Z, Q and X may be the same or different, respectively.

When the polymer (A) contains the structural unit represented by the general formula (E), the ratio of the structural unit represented by the general formula (E) in all the structural units contained in the Chain of the polymer (A) is preferably 1 It is -12 mol%, More preferably, it is 2-9 mol%.

When the polymer (A) contains a structural unit represented by the general formula (EE), the ratio of the structural unit represented by the general formula (EE) in all the structural units contained in the Chain of the polymer (A) is preferably 1. It is -10 mol%, More preferably, it is 2-8 mol%.

The Chain of the polymer (A) of the present embodiment may further contain a structural unit represented by the following general formula (M) in order to adjust the solubility of the polymer (A) in a solvent or the like.

[Formula 20]

When the polymer (A) contains the structural unit represented by the general formula (M), the ratio of the structural unit represented by the general formula (M) in all the structural units contained in the Chain of the polymer (A) is preferably 1. It is -15 mol%, More preferably, it is 2-10 mol%.

The chain of the polymer represented by the general formula (P) of the present embodiment may contain a divalent structural unit derived from a copolymerizable compound having a double bond.

Structural units include, for example, substituted or unsubstituted indene, maleimide, styrene, acenaphthylene, norbornadiene, dihydrofuran, terpene compounds (eg, pinene, limonene, etc.), linear alkenes ( For example, pentene, etc.), cyclic alkenes (cyclohexene, etc.), cyclododecatriene, tricycloundecaene, dialkyl fumarate (eg, dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin , (meth) acrylic acid compound (eg, methyl methacrylate, methyl acrylate), vinyl acetate, at least one structure derived from vinyl ether (eg, 2-hydroxyethyl vinyl ether, etc.) contains units.

As a substituent which these monomers may have, an alkyl group, an aryl group, etc. are mentioned. More specifically, examples of the substituted indene include methyl indene and the like. As a substituted maleimide, cyclohexyl maleimide, a phenyl maleimide, etc. are mentioned. As substituted styrene, methyl styrene, vinyltoluene, etc. are mentioned.

Among them, Chain is preferably a structural unit represented by General Formula (1) (a divalent structural unit derived from substituted or unsubstituted indene) and a structural unit represented by General Formula (2) (substituted or unsubstituted maleimide). a divalent structural unit derived from), a structural unit represented by the general formula (3) (a divalent structural unit derived from substituted or unsubstituted styrene), or a structural unit represented by the general formula (4) (substituted or unsubstituted) of a divalent structural unit derived from nobonadiene).

[Formula 21]

In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group. In General Formula (2), R ³ represents a hydrogen atom, an alkyl group or an aryl group. In the general formula (3), R ⁴ to R ⁶ each independently represent a hydrogen atom, an alkyl group or an aryl group. In the general formula (4), R ⁷ to R ¹⁰ each independently represent a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms.

In general formula (P), Y is a monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms derived from a compound containing a bifunctional or higher thiol group.

In the present embodiment, the number of functional groups is the number of thiol groups. That is, the thiol group-containing compound includes two or more thiol groups, and the organic group (i) is bonded to Chain through 1 to 6 thioether groups derived from the thiol groups. The organic group (i) may have a thiol group that is not involved in bonding with Chain, and the polymer (A) can be obtained as a mixture of each resin having n number (bonding number) of 1 to 6. .

The said organic group (i) of 1 or more and 30 or less carbon atoms is bifunctional or more, Preferably it is trifunctional or more. Although the upper limit is not particularly limited, it is hexafunctional or less.

The valence of the organic group (i) having 1 to 30 carbon atoms is 1 to 6, preferably 2 to 6, more preferably 3 to 6, from the viewpoint of the effect of the present invention.

The monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms may contain one or more atoms selected from O, N, S, P and Si. Examples of the 1-6 valent organic group (i) having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, and an alkyne group having 1 to 6 thioether groups (-S-* (* denotes a bond)). diyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups and heterocyclic groups.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, hep A ethyl group, an octyl group, a nonyl group, and a decyl group are mentioned. As an alkenyl group, an allyl group, a pentenyl group, and a vinyl group are mentioned, for example.

As an alkynyl group, ethynyl group is mentioned.

As an alkylidene group, a methylidene group and an ethylidene group are mentioned, for example. As an aryl group, a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group are mentioned, for example.

As an aralkyl group, a benzyl group and a phenethyl group are mentioned, for example.

As an alkaryl group, a tolyl group and a xylyl group are mentioned, for example.

As a cycloalkyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are mentioned, for example.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, isobutoxy group, t-butoxy group, n-pentyloxy group, A neopentyloxy group and n-hexyloxy group are mentioned.

As a heterocyclic group, an epoxy group and an oxetanyl group are mentioned, for example.

Examples of the bifunctional or higher thiol group-containing compound include compounds represented by the following formulas (s-1) to (s-21).

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

In the present embodiment, the difunctional or higher functional thiol group-containing compound preferably includes a trifunctional or higher functional thiol group-containing compound from the viewpoint of the effect of the present invention. Also, the thiol group-containing compound preferably has an ester structure.

In the present embodiment, the bifunctional or higher thiol group-containing compound is among the compounds represented by the formulas (s-1) to (s-21), the formulas (s-1) to (s-3), (s- 5) and (s-8) to (s-10) more preferably include compounds represented by formulas (s-1) to (s-3), (s-5) and (s-9) It is particularly more preferable to include the compound shown.

The bifunctional or higher thiol group-containing compound may be used alone or in combination of two or more.

The organic group (i) having 1 to 6 valent carbon atoms and having 1 to 30 carbon atoms has at its terminal a thioether group (-S-* (* indicates a bond)) derived from the thiol group of these thiol group-containing compounds, and It is bonded to the structural unit included in the chain through the Oether group. The organic group (i) may have a thiol group not involved in bonding with Chain.

In the general formula (P), structures other than Chain may be bonded to Y. Specifically, the general formula (P) can be represented by the following general formula (P').

[Formula 43]

In the general formula (P'), Chain and Y have the same meaning as in the 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 1 to 6.

Q, which is a structure other than Chain, is not particularly limited as long as it can bind to Y, and various components used in the synthesis reaction can be cited. For example, the structural unit represented by the above general formula (AE) (the above general formula ( DE) and/or the structural unit represented by the general formula (SE)), the structural unit represented by the general formula (D), the structural unit represented by the general formula (S), the structural unit represented by the general formula (NB) At least one member selected from the structural unit represented by the general formula (MA), and a divalent structural unit derived from a copolymerizable compound having a double bond, or a group derived from the bifunctional or higher thiol group-containing compound can be heard

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

[Formula 44]

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

p is greater than 0, and is preferably 0.25 to 0.75.

q is greater than 0, preferably 0.25 to 0.75.

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

p, q or r may be the same or different for each structural unit in n [].

n is an integer of 1-6.

X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms. The organic group having 1 to 30 carbon atoms is the same as the organic group having 1 to 30 carbon atoms constituting R ¹ to R ⁴ in the general formula (NB).

Y is the above-mentioned organic group (i) having 1 to 6 valent carbon atoms and 1 to 30 carbon atoms derived from a compound containing a bifunctional or higher thiol group; combine

A contains the structural unit represented by the said general formula (NB).

B contains the structural unit represented by the said general formula (AE). In this embodiment, at least one kind of structural unit selected from the structural units represented by the said general formula (DE) and the said general formula (SE) can be included.

B is also, if necessary, 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) At least one kind of structural unit selected from the structural units shown may be included.

C contains a structural unit derived from the above copolymerizable compound having a double bond.

A plurality of A's, B's, or C's may be the same or different.

In the general formula (P1), the bonding order of A, B and C is not particularly limited, and any of A, B and C may be bonded to Y.

In the general formula (P1), Y may be bonded to structures other than the polymer chain represented by []n. Specifically, the general formula (P1) can be represented by the following general formula (P1').

[Formula 45]

In 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 1 to 6.

The polymer (A) of the present embodiment, when the compound represented by the above formula (s-2) is used as the bifunctional or higher thiol group-containing compound, for example, has a structure represented by the following general formula (I) can have

[Formula 46]

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

In the general formula (I), the bonding order of A, B and C is not particularly limited, and any of A, B and C may be bonded to a thioether group. Further, in the general formula (I), although shown by an example in which four structural units in [ ] are bonded through thioether groups derived from the four mercapto groups of the compound represented by the general formula (s-2), A structure in which 1 to 3 structural units in [ ] are bonded may be used. In the present embodiment, the polymer (A) can be obtained as a mixture containing at least one compound in which 1 to 4 structures in [ ] are bonded.

The weight average molecular weight Mw of the polymer (A) is, for example, 1,000 to 20,000, preferably 1,500 to 17,500, more preferably 2,000 to 15,000, still more preferably 3,000 to 10,000. By appropriately adjusting the weight average molecular weight, sensitivity and solubility to an alkaline developer can be adjusted.

The degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of the polymer (A) is preferably 1.0 to 6.0, more preferably 1.0 to 5.5, still more preferably 1.0 to 5.0. By appropriately adjusting the degree of dispersion, the physical properties of the polymer (A) can be made homogeneous, which is preferable. In addition, these values can be obtained by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

The glass transition temperature of the polymer (A) is preferably 150 to 250°C, more preferably 170 to 230°C. Polymer (A) has a relatively high glass transition temperature by containing the structural unit represented by general formula (NB) mainly. This is preferable in that a pattern formed on a substrate can stably exist in the manufacture of a liquid crystal display device or a solid-state imaging device. In addition, a glass transition temperature can be calculated|required by differential thermal analysis (DTA), for example.

The content (ratio) of each structural unit contained in the polymer (A) of the present embodiment is the input amount (molar amount) of the raw material at the time of polymer synthesis, the amount of the raw material remaining after synthesis, and the peak area of various spectra (eg, peak area of ¹ H-NMR), etc., can be estimated/calculated.

<Method for producing polymer (A)>

The manufacturing method of the polymer (A) of this embodiment is demonstrated.

Polymer (A) can be manufactured (synthesized) by any method. Polymer (A), for example,

Step (I): preparing a raw material polymer containing a structural unit represented by the general formula (NB), a structural unit represented by the general formula (MA), and the above organic group (i) having 1 to 6 valent carbon atoms and 30 or less carbon atoms process to do,

Step (II): The raw material polymer obtained in step (I), a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as "polyfunctional (meth)acrylic monomer"), and/or A structural unit represented by the general formula (NB) by reacting a compound having a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acrylic monomer") in the presence of a basic catalyst; The organic group (i) having 1 to 6 valent carbon atoms and 30 or less carbon atoms, the structural unit represented by the general formula (D) and/or the structural unit represented by the general formula (S), and in some cases, the structure represented by the general formula (MA) A step of preparing a polymer precursor containing units, and

Step (III): The polymer precursor obtained in Step (II) is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to form a structural unit represented by the general formula (NB) having 1 to 6 carbon atoms and 30 or less. The organic group of (i), the structural unit represented by the general formula (D) and / or the structural unit represented by the general formula (S), the structural unit represented by the general formula (AE) (the structural unit represented by the general formula (DE) and / or a structural unit represented by the general formula (SE)), optionally a structural unit represented by the general formula (MA).

In step (II), when both a polyfunctional (meth)acrylic monomer and a monofunctional (meth)acrylic monomer are used, the polyfunctional (meth)acrylic monomer is first reacted with the raw material polymer, and the reaction mixture obtained is It is preferable to react a functional (meth)acrylic monomer.

(Process (I))

A raw material containing the structural unit represented by the general formula (NB), the structural unit represented by the general formula (MA), and the organic group (i) having 1 to 6 valent carbon atoms and 1 to 30 carbon atoms in step (I). The step of preparing the polymer can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by the general formula (NBm) and maleic anhydride in the presence of the bifunctional or higher thiol group-containing compound. In addition, the definitions of R ¹ , R ² , R ³ and R ⁴ and a1 in the general formula (NBm) are the same as those in the general formula (NB). It is the same also about a preferable aspect.

[Formula 47]

As a monomer represented by general formula (NBm), for example, 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-phenethyl- 2-norbornene, 2-acetyl-5-norbornene, 5-norbornene-2-carboxylic acid methyl, 5-norbornene-2,3-dicarboxylic acid anhydride, and the like. At the time of polymerization, the monomer represented by general formula (NBm) may be used alone or in combination of two or more.

The monomer composition may contain other monomers in addition to the above monomers.

The other monomer is not particularly limited as long as it is a copolymerizable compound having a double bond, and a known compound can be used, and can be polymerized with a monomer represented by the general formula (NBm) and maleic anhydride. Examples of other monomers include substituted or unsubstituted indene, maleimide, styrene, acenaphthylene, norbornadiene, dihydrofuran, terpene compounds (eg, pinene, limonene, etc.), linear alkenes ( For example, pentene, etc.), cyclic alkenes (cyclohexene, etc.), cyclododecatriene, tricycloundecaene, dialkyl fumarate (eg, dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin , (meth)acrylic acid compounds (eg, methyl methacrylate, methyl acrylate), vinyl acetate, vinyl ethers (eg, 2-hydroxyethyl vinyl ether, etc.), and the like. In step (I), the monomer represented by the general formula (NBm), maleic anhydride, and further, if necessary, other monomers can be polymerized (addition polymerization) in the presence of the bifunctional or higher thiol group-containing compound. there is.

Examples of the bifunctional or higher thiol group-containing compound include, but are not limited to, compounds represented by the above formulas (s-1) to (s-21). The bifunctional or higher thiol group-containing compound may be used alone or in combination of two or more.

Although it does not limit about the polymerization method, Radical polymerization using a radical polymerization initiator is preferable. As a polymerization initiator, an azo compound, an organic peroxide, etc. can be used, for example.

Specifically as an azo compound, azobisisobutyronitrile (AIBN), dimethyl 2,2'- azobis (2-methylpropionate), 1,1'- azobis (cyclohexane carbonitrile) (ABCN) and the like.

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

About a polymerization initiator, only 1 type may be used and you may use it in combination of 2 or more type.

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

In the synthesis of the raw material polymer, the monomer represented by the general formula (NBm), maleic anhydride, and the polymerization initiator are dissolved in a solvent, put into a reaction vessel, and then heated, while adding the difunctional or higher thiol group-containing compound dropwise, It is carried out by advancing addition polymerization. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours.

It is preferable that the molar ratio of the monomer represented by general formula (NBm) and maleic anhydride at the time of charging into reaction container is 0.5:1 to 1:0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 1:1.

Through such a process, a "raw polymer" can be obtained.

In addition, any of a random copolymer, an alternating copolymer, a block copolymer, and a periodic copolymer may be sufficient as the raw material polymer. It is typically a random or alternating copolymer. Also, maleic anhydride is generally known as a monomer with strong alternating copolymerizability.

Further, after the synthesis of the raw material polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and remaining polymerization initiators may be performed.

Specifically, the synthesized raw material polymer and the organic phase containing the low molecular weight component are concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. And this solution is mixed with a poor solvent, such as methanol, and a monomer is precipitated. By filtering and drying this precipitate, the purity of the raw material polymer can be increased.

(Process (II))

A structure represented by the general formula (MA) contained in the raw material polymer by reacting the raw material polymer obtained in step (I) with the polyfunctional (meth)acrylic monomer and/or monofunctional (meth)acrylic monomer in the presence of a basic catalyst. A part of the unit is ring-opened to form a structural unit represented by the general formula (D) and/or a structural unit represented by the general formula (S), and a structural unit represented by the general formula (NB), 1 to 6 valent carbon atoms 1 or more 30 containing the organic group (i) below and the structural unit represented by the general formula (D) and/or the structural unit represented by the general formula (S), optionally including the structural unit represented by the general formula (MA) A polymer precursor is obtained.

More specifically, first, a solution in which a raw material polymer is dissolved in an appropriate organic solvent is prepared. Examples of organic solvents include methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF), and the like. A single solvent or mixed solvent may be used, but it is not limited thereto, and various organic solvents used in the synthesis of organic compounds or polymers may be used.

When obtaining a polymer containing both the structural unit represented by the general formula (NB) and the structural unit represented by the general formula (D) and the structural unit represented by the general formula (S), the polyfunctional Add (meth)acrylic monomer. Also, a basic catalyst is added. Then, the solution is appropriately mixed to obtain a uniform solution, so that at least the structural unit of the general formula (NB) and the structural unit of the general formula (D) are composed of 1 to 6 carbon atoms and the organic group (i) having 1 to 30 carbon atoms. A polymer having a structure bonded through a thioether group is obtained (step (II-i)).

Examples of the polyfunctional (meth)acrylic monomer that can be used here include compounds represented by the general formula (1b-m), compounds represented by the general formula (1c-m), and compounds represented by the general formula (1d-m). can be heard The definitions and specific aspects of k, R, X ¹ , X ¹ ′ and X ² in the general formula (1b-m) are the same as those in the above-described general formula (1b). Further, the definitions and specific aspects of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in the general formula (1c-m) are the same as in the general formula (1c) described above. same. n in the general formula (1c-m) is the same as that in the above general formula (1d).

[Formula 48]

[Formula 49]

[Formula 50]

As a polyfunctional (meth)acrylic compound having a hydroxyl group, those that can be preferably used are shown below. In addition, those 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.

[Formula 51]

[Formula 52]

[Formula 53]

[Formula 54]

[Formula 55]

[Formula 56]

Next, by reacting the monofunctional (meth)acrylic monomer with the polymer obtained in step (II-i) in the presence of a basic catalyst, at least the structural unit of the general formula (NB), the structural unit of the general formula (D), and A polymer precursor containing a structure in which the structural unit of the general formula (S) is bonded to the organic group (i) having 1 to 30 carbon atoms through 1 to 6 thioether groups can be obtained (step (II-ii) )).

As the basic catalyst, an amine compound, a nitrogen-containing heterocyclic compound, or the like 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 the basic catalyst used can be, for example, about 10 to 60 parts by mass with respect to 100 parts by mass of the raw material polymer. Note that, when an excessive amount of basic catalyst is used, the amount of acid required for neutralization increases, and there is a possibility that purification becomes complicated.

By heating the solution, preferably at 60 to 80° C., for about 3 to 9 hours, ring-opening of the structural unit of the general formula (MA) contained in the raw material polymer/structural unit of the general formula (AE) is formed.

Further, for example, in the middle of the above heating, by additionally adding a monofunctional (meth)acrylic compound having a hydroxyl group to the reaction system, the structural unit represented by the above-mentioned general formula (SE) in the polymer (A) can be generated. there is.

In view of the steric hindrance of the reaction, a monofunctional (meth)acrylic compound having a hydroxyl group tends to react more easily with the raw material polymer than a polyfunctional (meth)acrylic compound having a hydroxyl group. Therefore, in the case of generating the structural unit represented by the above-mentioned general formula (SE) in the polymer (A), a monofunctional (meth)acrylic compound having a hydroxyl group is not introduced into the reaction system from the beginning, but additionally added into the reaction system desirable.

As a monofunctional (meth)acryl compound which has a hydroxyl group, the compound represented by the following general formula (Sa-m) is mentioned, for example.

In the general formula (Sa-m), the definitions of X ¹⁰ and R are the same as those in the general formula (Sa).

[Formula 57]

Specific examples of the compound represented by the general formula (Sa-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acryl. Rate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl -2-hydroxyethyl-phthalic acid etc. are mentioned.

Any one of the structural unit represented by the general formula (NB), the organic group (i) having 1 to 6 valent carbon atoms and 30 or less carbon atoms, and the structural unit represented by the general formula (AE) and the structural unit represented by the general formula (DE) When obtaining a polymer containing , after step (I), only either one of step (II-i) and step (II-ii) may be performed.

(Process (III))

The polymer precursor obtained in step (II) is reacted with an epoxy group-containing (meth)acryl compound in the presence of a catalyst, and the reaction between the carboxyl group of the polymer precursor and the epoxy group of the epoxy group-containing (meth)acryl compound results in a general formula (AE ) (a structural unit represented by the general formula (DE) and/or a structural unit represented by the general formula (SE)) is formed, and a structural unit represented by the general formula (NB), 1 to 6 valent carbon atoms 1 or more 30 The organic group (i) below, the structural unit represented by the general formula (D) and/or the structural unit represented by the general formula (S), the structural unit represented by the general formula (AE) (the structural unit represented by the general formula (DE) and/or a structural unit represented by the general formula (SE)), and optionally a structural unit represented by the general formula (MA) (A) is prepared.

Step (III) is preferably performed by further adding an epoxy group-containing (meth)acrylic compound to the reaction system containing the polymer precursor obtained in step (II-ii).

The reaction between the polymer precursor and the epoxy group-containing (meth)acrylic compound proceeds in the presence of a basic catalyst. As the basic catalyst, a catalyst remaining in the reaction system obtained in step (II-ii) can be used as it is. Therefore, in step (III), the polymer precursor is isolated and purified from the reaction mixture containing the polymer precursor obtained in step (II-ii), or the basic catalyst contained in the mixture is not neutralized, and the process is performed as it is. It is preferable to carry out by further adding an epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor obtained in (II-ii).

Specifically, by heating a reaction solution obtained by further adding an epoxy group-containing (meth)acrylic compound to a reaction mixture containing a polymer precursor, preferably at 60 to 80° C. for about 1 to 9 hours, the carboxyl group of the polymer precursor is heated. By the reaction of the epoxy group of the epoxy group-containing (meth)acrylic compound, a structural unit represented by the general formula (AE) (a structural unit represented by the general formula (DE) and/or a structural unit represented by the general formula (SE)) is formed, , polymer (A) is produced.

Examples of the epoxy group-containing (meth)acrylic compound include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexylmethyl acrylate, 3,4- Epoxy cyclohexyl methyl methacrylate, glycidyl acrylate, etc. are mentioned, and 1 type(s) or 2 or more types selected from these can be used.

The addition amount of the epoxy group-containing (meth)acrylic compound is preferably 0.1 to 3.0 moles per mole of the carboxyl group of the polymer precursor.

Further, between step (II) and step (III), by treating the polymer precursor obtained in step (II) with water in the presence of a catalyst, the structural unit represented by the formula (MA) contained in the polymer precursor is ring-opened, , It is also preferable to include the process (II') of forming the structural unit represented by Formula (M).

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

In the step (II'), water is added to the reaction system containing the polymer precursor P, and the resulting reaction solution is heated, preferably at 60 to 80°C for about 0.25 to 6 hours, to be included in the polymer precursor P. The structural unit of formula (MA) to be ring-opened, and the structural unit represented by formula (M) is produced|generated. This reaction proceeds in the presence of a basic catalyst. As the basic catalyst, a catalyst remaining in the reaction system obtained in step (II) can be used as it is. Therefore, in the step (II), the polymer precursor P is isolated and purified from the reaction mixture containing the polymer precursor P obtained in step (II), or the basic catalyst contained in the mixture is not neutralized. ) It is preferable to carry out by additionally adding water to the reaction mixture containing the polymer precursor P obtained in.

Next, the polymer precursor obtained in step (II') can be used for reaction in step (III). In step (III), the polymer precursor obtained in step (II') is reacted with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst to obtain a carboxyl group of the polymer precursor and an epoxy group of the epoxy group-containing (meth)acrylic compound. By the reaction, a structural unit represented by the general formula (AE) (a structural unit represented by the general formula (DE) and/or a structural unit represented by the general formula (SE)) is formed, and a structural unit represented by the general formula (NB); The organic group (i) having 1 to 6 valent carbon atoms and 30 or less carbon atoms, the structural unit represented by the general formula (D) and/or the structural unit represented by the general formula (S), the structural unit represented by the general formula (AE) (general structural unit represented by formula (DE) and/or structural unit represented by general formula (SE)), optionally structural unit represented by general formula (MA), structural unit represented by general formula (E) and/or general formula ( A polymer (A') containing a structural unit represented by EE) can be prepared.

After the step (III), it is preferable to further perform the following steps appropriately for the purpose of removing unnecessary components other than the desired polymer (A).

First, the reaction solution obtained by diluting with an organic solvent and adding an acid (for example, formic acid, citric acid, etc.) is vigorously stirred in a separatory funnel for at least 3 minutes. This is stopped for 30 minutes or more, divided into an organic phase and a water phase, and the water phase is removed. In this way, an organic solution of the polymer (A) is obtained.

An excess amount of toluene is added to the resulting organic solution of the polymer (A) to reprecipitate the polymer (A). Further, the polymer powder obtained by reprecipitation is further washed with toluene several times (for example, twice).

Further, for removal of the acid or basic catalyst, an operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (for example, three times).

The high-purity polymer (A) of the present embodiment can be obtained by drying the polymer powder after washing with ion-exchanged water at, for example, 30 to 60°C for 16 hours or longer.

In this embodiment, by further adding water to the polymer (A) in the same manner as in step (II'), the structural unit of the formula (MA) contained in the polymer (A) is ring-opened to form the formula (M). It is also desirable to create structural units that appear. In this step, the solubility of the polymer (A) in a solvent or the like can be adjusted.

(Polymer solution containing polymer (A))

The polymer solution of this embodiment contains the polymer (A) mentioned above.

The polymer solution of the present embodiment may contain, together with the polymer (A), a compound (B) having a thiol group and an alkoxy group or an oligomer thereof.

As the compound (B), as long as it has a thiol group and an alkoxy group, known compounds can be used within the scope of exhibiting the effects of the present invention.

The polymer solution of the present embodiment can provide a cured resin product having excellent adhesion to a substrate or the like by containing the compound (B) or an oligomer thereof. Although it does not specifically limit as a board|substrate, As mentioned later, a glass substrate, a silicon wafer, a ceramic board|substrate, an aluminum board|substrate, a SiC wafer, a GaN wafer, a copper clad laminated board etc. are mentioned, for example.

In this embodiment, it is preferable that the alkoxy group contained in compound (B) is a C1-C3 alkoxy group from a viewpoint of the effect of this invention, and one or more atoms selected from O, N, S, P, and Si It is also preferable to have a structure in which a thiol group and an alkoxy group are bonded to an organic chain which may contain.

Specifically, it is preferable that the compound (B) includes a compound represented by the following general formula (a).

[Formula 58]

In the general formula (a), R each 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 R's are alkoxy groups having 1 to 3 carbon atoms.

L represents an m+n valent organic chain which may contain one or more atoms selected from O, N, S, P and Si.

In the present embodiment, the m+n valent organic chain of L is m derived from a straight-chain or branched alkylene group having 1 to 10 carbon atoms (m+n: 2) or a straight-chain or branched alkane having 1 to 20 carbon atoms. +n valent groups, and m+n valent groups derived from substituted or unsubstituted siloxanes.

X represents a divalent organic group which may contain a single bond or a carbonyl group, a (thio)ester group or a (thio)amide group.

In this embodiment, as X, a single bond or a C1-C10 alkylene ester group is preferable.

Q represents a divalent organic group which may contain a single bond or a carbonyl group, a (thio)ester group, or a (thio)amide group.

In this embodiment, as Q, a single bond or a C1-C10 alkylene ester group is preferable.

m:n (molar ratio) is 1:1 to 1:8, and m+n is 2 to 20.

The weight average molecular weight of the compound is 100 to 2000.

As the compound (B), 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, polyfunctional silane coupling agent containing siloxene printing (KR-519, manufactured by Shin-Etsu Silicone Co., Ltd.), organic chain-containing multifunctional silane coupling agent having the following structural units, and the like. can

[Formula 59]

In the above general formula, a:b (molar ratio) is 2:1 to 4:1. The weight average molecular weight is 1000-1500. * is a bonding hand. As the said compound, X-12-1154 (made by Shin-Etsu Silicone Co., Ltd.) etc. are mentioned.

Moreover, a compound (B) or its oligomer may be used individually by 1 type, and may mix and use 2 or more types.

In the polymer solution of the present embodiment, the compound (B) or oligomer thereof is 0.25 to 20% by mass, preferably 1.0 to 15% by mass, based on the polymer (A) from the viewpoint of the effect of the present invention. , More preferably, it is 2.0-12 mass %.

Further, within a range that does not affect the effects of the present invention, the polymer solution may contain at least one selected from polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds.

[Multifunctional (meth)acrylic compound]

As the polyfunctional (meth)acrylate compound, which is a compound having two or more (meth)acryloyl groups, conventionally known compounds can be used as long as the effects of the present invention can be exhibited.

As a polyfunctional (meth)acrylic compound, the compound represented by the following general formula (1b-p), the compound represented by general formula (1c-p), and the compound represented by general formula (1d-p) are mentioned, for example. may, but are not limited to these.

The definitions and specific aspects of k, R, X ¹ , X ¹ ′ and X ² in the general formula (1b-p) are the same as those in the above-described general formula (1b). Further, the definitions and specific aspects of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in the general formula (1c-p) are those in the above-mentioned general formula (1c) same.

Y in general formula (1b-p), general formula (1c-p), and general formula (1d-p) is a hydrogen atom or a (meth)acryloyl group, or a combination thereof.

In the general formula (1b-p), the general formula (1c-p) and the general formula (1d-p), the compound in which Y is a hydrogen atom is an unreacted monomer (ie, the general formula (1b-p), the general formula ( 1c-p) and the compound represented by the general formula (1d-p)) may be used, and may be separately added.

n in the general formula (1d-p) is an integer of 2 or greater, preferably an integer of 2 to 5, more preferably an integer of 2 to 3.

[Formula 60]

[Formula 61]

[Formula 62]

Although the compound of the following structure is mentioned as a specific example of the polyfunctional (meth)acryl compound represented by General formula (1b-p), It is not limited to these. In addition, in the following compounds, Y represents a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[Formula 63]

[Formula 64]

[Formula 65]

Although the following compounds are mentioned as a specific example of the polyfunctional (meth)acryl compound represented by general formula (1c-p), it is not limited to these.

[Formula 66]

[Formula 67]

[Formula 68]

In the polymer solution of the present embodiment, the polyfunctional (meth)acrylic compound can be blended within a range that does not affect the effect of the present invention, and in the gel permeation chromatography (GPC) chart of the resin composition The peak area derived from the polyfunctional (meth)acrylic compound is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less with respect to the peak area of the resin. can

[Monofunctional (meth)acrylic compound]

The polymer solution of this embodiment may contain a monofunctional (meth)acrylic compound which is a compound having one (meth)acryloyl group.

As a monofunctional (meth)acrylic compound, the compound represented by the following general formula (Sa-m) is mentioned. The monofunctional (meth)acrylic compound may be an unreacted monomer or may be added separately.

In the general formula (Sa-m), the definitions of X ¹⁰ and R are the same as those in the general formula (Sa).

[Formula 69]

Specific examples of the compound represented by the general formula (Sa-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acryl. Rate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl -2-hydroxyethyl-phthalic acid etc. are mentioned.

In the polymer solution of the present embodiment, the monofunctional (meth)acrylic compound can be blended within a range that does not affect the effect of the present invention, and in the gel permeation chromatography (GPC) chart of the resin composition The peak area derived from the monofunctional (meth)acrylic compound can be blended in an amount such that the peak area of the resin is preferably 10% or less, more preferably 5% or less, still more preferably 2% or less. there is.

The polymer solution of the present embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. As the organic solvent, one or two or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, and carbonate-based solvents can be used.

Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, and cyclohexanone. These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

(Preparation of polymer solution)

The polymer solution of this embodiment can be produced by mixing the above components by a known method. The polymer solution of this embodiment is used as a resin material of the photosensitive resin composition described below.

<Photosensitive resin composition>

The photosensitive resin composition of this embodiment contains the polymer mentioned above, the polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic 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 mentioned above, and a photosensitizer. Each component is demonstrated below.

[Photosensitizer]

As a photosensitizer used for the photosensitive resin composition of this embodiment, a radical photopolymerization initiator is mentioned. As the photoradical polymerization initiator, known compounds can be used, such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenylketone. , 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-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4- Methylthiophenyl)-2-morpholinopropan1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)- Alkylphenone compounds such as 2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone; benzoin-based compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Thioxanthone systems such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone compound; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(triazine) halomethylated triazine compounds such as chloromethyl)-s-triazine; 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3 halomethylated oxadiazole-based compounds such as 4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5' -biimidazole-based compounds such as tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H Oxime ester-type compounds, such as -carbazol-3-yl] -1-(O-acetyl oxime); titanocene-based compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine-based compounds such as 9-phenylacridine; etc. can be mentioned. Radical photopolymerization initiators may be used individually by 1 type, or may be used in combination of 2 or more type.

The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, based on 100 parts by mass of the polymer.

The photosensitive resin composition of this embodiment has excellent alkali solubility while having high sensitivity in photolithography processing by including the said component. Therefore, the photosensitive resin composition has excellent developability and excellent processability in the photolithography method. Moreover, since yellowing of the photosensitive resin composition is suppressed, the article obtained by hardening the said photosensitive resin composition has transparency.

The photosensitive resin composition of the present embodiment may also contain a compound having one (meth)acryloyl group (monofunctional (meth)acrylic compound) in addition to the above-described polymer, polyfunctional (meth)acrylic compound, and photosensitizer. Monofunctional (meth)acrylic compounds are the same as those described above. By including a monofunctional (meth)acrylic compound, the alkali solubility of the photosensitive resin composition obtained further improves and yellowing is reduced.

As one aspect, the photosensitive resin composition may also contain a coloring agent. By containing a coloring agent, it can use suitably as a formation material of the color filter of a liquid crystal display device or a solid-state image sensor. As the colorant, various pigments or dyes can be used.

As a pigment, an organic pigment or an inorganic pigment can be used.

Examples of organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, Anthraquinone-based pigments, quinophthalone-based pigments, metal complex-based pigments, diketopyrrolopyrrole-based pigments, xanthene-based pigments, pyrromethene-based pigments, dye lake-based pigments, and the like can be used.

Examples of inorganic pigments include white body pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), oil pigments (chromium yellow, cadminium-based, chromium vermilion, nickel titanium, chromium titanium, Yellow iron oxide, Bengala, zinc chromate, lead, ultramarine blue, Prussian blue, cobalt blue, chromium green, chromium oxide, bismuth vanadate, etc.), bright material pigments (pearl pigment, aluminum pigment, bronze pigment, etc.), fluorescence Pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.

As a dye, the well-known dye described in Unexamined-Japanese-Patent No. 2003-270428, Unexamined-Japanese-Patent No. 9-171108, Unexamined-Japanese-Patent No. 2008-50599 etc. can be used, for example.

When the photosensitive resin composition contains a coloring agent, the photosensitive resin composition may contain only 1 type of coloring agents, and may also contain 2 or more types.

As the colorant (particularly pigment), those having an appropriate average particle diameter can be used depending on the purpose or use, but when transparency such as a color filter is required in particular, a small average particle diameter of 0.1 μm or less is preferable, and other paints When the concealment property of the back is required, a large average particle diameter of 0.5 μm or more is preferable.

The colorant may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose or application.

When the photosensitive resin composition contains a colorant, the amount may be appropriately set according to the purpose or use, but from the viewpoint of coexistence of color concentration and dispersion stability of the colorant, with respect to the entire non-volatile component (components excluding the solvent) of the photosensitive resin composition , Preferably it is 3-70 mass %, More preferably, it is 5-60 mass %, More preferably, it is 10-50 mass %.

(Surfactants)

The photosensitive resin composition of this embodiment can contain surfactant, and a nonionic surfactant is preferable as surfactant.

By including the nonionic surfactant, the applicability at the time of applying the photosensitive resin composition onto a substrate to obtain a resin film is improved, and a coating film having a uniform thickness can be obtained. In addition, it is possible to prevent residue and pattern floating during development of the coated film.

The nonionic surfactant is, for example, a compound containing a fluorine group (for example, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a main skeleton. In this embodiment, it is more preferable to use a nonionic surfactant containing a fluorochemical surfactant or a silicone surfactant, and it is particularly preferable to use a fluorochemical surfactant. As the fluorine-based surfactant, for example, Megafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F-482, F-477, F- 554, F-556 and F-557, Novec FC4430 and FC4432 manufactured by Sumitomo 3M Co., Ltd., and the like, but are not limited thereto.

As a compounding quantity of surfactant in the case of using surfactant, 0.01-10 weight% is preferable with respect to 100 mass parts of resin.

(solvent)

The photosensitive resin composition can typically contain a solvent. As the solvent, an organic solvent is preferably used. Specifically, one or two or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, and carbonate-based solvents can be used.

Examples of the solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N -Methylpyrrolidone (NMP), methyl-n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclo hexanone, or mixtures thereof.

Although the amount of the solvent used is not particularly limited, it is used in an amount such that the concentration of the non-volatile component is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

(shading agent)

The resin composition of this embodiment may contain a light-shielding agent. The photosensitive resin composition may contain only 1 type of light-shielding agent, and may also contain 2 or more types.

When the photosensitive resin composition contains a light-shielding agent, the amount may be appropriately set according to the purpose or use, but from the viewpoint of coexistence of light-shielding performance and dispersion stability of the light-shielding agent, all non-volatile components (components excluding the solvent) of the photosensitive resin composition With respect to , it is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass.

(crosslinking agent)

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

The crosslinking agent is not particularly limited as long as it is capable of crosslinking the polymer (can chemically bond with the polymer) by the action of active species generated from the photopolymerization initiator.

The crosslinking agent may not chemically bond only with the polymer, but may react with each other to form a bond.

The crosslinking agent is, for example, preferably a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule. (However, a crosslinking agent does not correspond to the polymer mentioned above). It is preferable to use a crosslinking agent having the same type of crosslinkable group as the crosslinkable group (polymerizable double bond) of the polymer from the standpoint of uniform curability and further improvement in sensitivity.

There is no particular upper limit on the number of functions (the number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, preferably 6 or less.

Specifically as a crosslinking agent, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate , butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkyl Renoxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate rate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide added trimethylolpropane tri(meth)acrylate, ethylene oxide added ditrimethylolpropane tetra( Meth)acrylate, ethylene oxide added Pentaerythritol tetra(meth)acrylate, ethylene oxide added dipentaerythritol hexa(meth)acrylate, propylene oxide added Trimethylolpropane tri(meth)acrylate, propylene oxide added Ditrimethylolpropane tetra(meth)acrylate, propylene oxide added pentaerythritol tetra(meth)acrylate, propylene oxide added dipentaerythritol hexa(meth)acrylate, ε-caprolactone added trimethylolpropane Ly(meth)acrylate, ε-caprolactone added ditrimethylolpropanetetra(meth)acrylate, ε-caprolactone added pentaerythritol tetra(meth)acrylate, ε-caprolactone added dipentaerythritol hexa polyfunctional (meth)acrylates such as (meth)acrylate;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexane diol Divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide added trimethylolpropane trivinyl ether, ethylene oxide added ditrimethylolpropane polyfunctional vinyl ethers such as tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether;

2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4- (meth)acrylate Vinyloxybutyl, (meth)acrylate 4-vinyloxycyclohexyl, (meth)acrylate 5-vinyloxypentyl, (meth)acrylate 6-vinyloxyhexyl, (meth)acrylate 4-vinyloxymethylcyclohexylmethyl, (meth)acrylate ) Contains vinyl ether groups such as p-vinyloxymethylphenylmethyl acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate (meth) acrylic acid esters;

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol Diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol penta allyl ether, dipentaerythritol hexaallyl ether, ethylene oxide addition trimethylolpropane triallyl ether, ethylene oxide addition ditrimethylol propane polyfunctional allyl ethers such as tetraallyl ether, ethylene oxide-added pentaerythritol tetra-allyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether;

(meth)acrylic acid esters containing an allyl group such as allyl (meth)acrylate;

Tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide addition tri (acryloyloxyethyl) isocyanurate, alkylene oxide addition tri ( polyfunctional (meth)acryloyl group-containing isocyanurates such as methacryloyloxyethyl)isocyanurate;

polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate;

Polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and 2-hydroxyethyl (meth)acrylate, 2-hydroxy (meth)acrylate polyfunctional urethane (meth)acrylates obtained by reaction with hydroxyl group-containing (meth)acrylic acid esters such as propyl;

polyfunctional aromatic vinyls such as divinylbenzene;

etc. can be mentioned.

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

When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only 1 type of crosslinking agent, and may also contain 2 or more types of crosslinking agents. What is necessary is just to set the quantity suitably according to the purpose or use, when the photosensitive resin composition contains a crosslinking agent. As an example, the amount of the crosslinking agent is usually 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, based on 100 parts by mass of the photosensitive resin composition.

The photosensitive resin composition may contain fillers, binder resins other than the above-mentioned polymers, acid generators, heat resistance improvers, developing aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, and gloss depending on various purposes and required characteristics. Components such as a removing agent, an antifoaming agent, a leveling agent, an antistatic agent, a dispersing agent, a slip agent, a surface modifier, a thixotropic agent, a thixotropic aid, a silane coupling agent, and a polyhydric phenol compound may also be included.

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

A film with a pattern can be obtained by forming a film using the photosensitive resin composition described above, exposing and developing the film to form a pattern. This film is applied to a color filter, a black matrix, or the like. That is, a color filter can be obtained by forming a pattern using the photosensitive resin composition containing a coloring agent. Moreover, a black matrix can be obtained by forming a pattern using the photosensitive resin composition containing a light-shielding agent. Then, a liquid crystal display device or a solid-state imaging device including a color filter or a black matrix can be manufactured.

A typical procedure for forming a pattern is described.

(Formation of photosensitive resin film)

For example, the photosensitive resin film is first obtained by applying the above photosensitive resin composition on an arbitrary substrate and drying it as necessary.

The substrate on which the composition is applied is not particularly limited. For example, glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, copper-clad laminates and the like are exemplified.

The substrate may be an unprocessed substrate or a substrate having electrodes and elements formed thereon. It may be surface treated to improve adhesion.

The application method of the photosensitive resin composition is not specifically limited. It can be performed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, inkjet method, or the like.

Drying of the photosensitive resin composition applied on the substrate is typically performed by heat treatment with a hot plate, hot air, oven or the like. The heating temperature is usually 80 to 140°C, preferably 90 to 120°C. Moreover, the heating time is usually 30 to 600 seconds, preferably about 30 to 300 seconds.

The film thickness of the photosensitive resin film is not particularly limited and may be appropriately adjusted according to the pattern to be finally obtained, but is usually 0.5 to 10 μm, preferably 1 to 5 μm. In addition, the film thickness can be adjusted by the content of the solvent in the photosensitive resin composition, the coating method, and the like.

(exposure)

Exposure is typically performed by irradiating the photosensitive resin film with actinic rays through an appropriate photomask.

As actinic rays, X-rays, electron beams, ultraviolet rays, visible rays, etc. are mentioned, for example. In terms of wavelength, light of 200 to 500 nm is preferable. From the viewpoint of pattern resolution and handleability, the light source is preferably g-ray, h-ray or i-ray of a mercury lamp, and i-ray is particularly preferred. Moreover, you may mix and use two or more light rays. As an exposure apparatus, a contact aligner, a mirror projection aligner, or a stepper is preferable.

The light amount of exposure may be appropriately adjusted according to the amount of the photosensitive agent in the photosensitive resin film, etc., but is, for example, about 100 to 500 mJ/cm ² .

In addition, you may heat the photosensitive resin film again after exposure, as needed (heating after exposure: Post Exposure Bake). The temperature is, for example, 70 to 150°C, preferably 90 to 120°C. Moreover, the time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. By heating after exposure, the reaction by radicals generated from the photoradical polymerization initiator is promoted, and the curing reaction is further promoted.

(phenomenon)

By developing the exposed photosensitive resin film with an appropriate developer, a pattern can be obtained and a substrate provided with a pattern can be manufactured.

Since the photosensitive resin film made of the photosensitive resin composition containing the polymer solution of the present embodiment has excellent adhesion to the substrate, peeling of the pattern is suppressed in the developing step.

In the developing step, development can be performed using a suitable developing solution, for example, using a method such as an immersion method, a puddle method, or a rotary spray method. By developing, the exposed part (in the case of positive type) or the unexposed part (in the case of negative type) of the photosensitive resin film is eluted and removed, and a pattern is obtained.

The usable developer is not particularly limited. For example, an aqueous alkali solution or an organic solvent can be used.

Specifically, as the aqueous alkali solution, (i) an aqueous solution of an inorganic alkali such as sodium hydroxide, sodium carbonate, sodium silicate, or ammonia; (ii) an aqueous solution of an organic amine such as ethylamine, diethylamine, triethylamine, or triethanolamine; ( iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide; and the like.

Since the polymer of the present embodiment has adjusted alkali solubility and excellent sensitivity, in the case of using a strongly basic developing solution such as TMAH (tetramethylammonium hydroxide) solution, the pattern after exposure and development has a shape as designed. can be done with

Specific examples of the organic solvent include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether solvents such as propylene glycol monomethyl ether. etc. can be mentioned.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the developing solution, for example.

In this embodiment, it is preferable to use aqueous alkali solution as a developing solution, and it is more preferable to use tetramethylammonium hydroxide, aqueous sodium carbonate solution, or aqueous potassium hydroxide solution.

The concentration of the aqueous alkali solution is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

Through the above steps, a pattern can be obtained/a substrate with a pattern can be manufactured, but various treatments may be performed after development.

For example, after development, the pattern and the substrate may be washed with a rinse liquid. Examples of the rinse liquid include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These may be used independently and may be used in combination of 2 or more type.

Moreover, you may make it harden sufficiently by heating the obtained pattern. The heating temperature is typically 150 to 400°C, preferably 160 to 300°C, and more preferably 200 to 250°C. Although the heating time is not particularly limited, it is within the range of 15 to 300 minutes, for example. This heat treatment can be performed by a hot plate, an oven, a heating oven capable of setting a temperature program, or the like. As atmospheric gas at the time of heat processing, air may be sufficient and an inert gas, such as nitrogen and argon, may be sufficient. Moreover, you may heat under reduced pressure.

Fig. 1 schematically shows an example of a structure of a liquid crystal display device and/or a solid-state imaging device including a color filter and/or a black matrix.

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

The substrate 10 is usually made of a material that transmits light, and is made of, for example, glass, polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin polymer, and the like. The substrate 10 may be subjected to corona discharge treatment, ozone treatment, chemical treatment, or the like, if necessary.

The substrate 10 is preferably made of glass.

The black matrix 11 is comprised by the hardened|cured material of the photosensitive resin composition containing a light-shielding agent, for example.

As the color filter 12, three colors of red, green, and blue usually exist. The color filter 12 is comprised by the hardened|cured material of the photosensitive resin composition containing the coloring agent according to each color.

As mentioned above, although embodiment of this invention was described, these are examples of this invention, and various structures other than the above are employable. In addition, the present invention is not limited to the above-described embodiment, and variations, improvements, and the like within the scope of achieving the object of the present invention are included in the present invention.

Example

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Compounds used in Examples may be indicated by the following abbreviations or trade names.

MA: maleic anhydride

NB: 2-norbornene

MEK: methyl ethyl ketone

PEMP: pentaerythritol tetrakis (3-mercaptopropionate), a compound represented by the following formula (s-2) (manufactured by SC Yuki Chemical Co., Ltd.)

[Formula 70]

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

[Formula 71]

DPMP: dipentaerythritol hexakis (3-mercaptopropionate), a compound represented by the following formula (s-3) (manufactured by SC Yuki Chemical Co., Ltd.)

[Formula 72]

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

[Formula 73]

Karenz MT PE-1: pentaerythritol tetrakis (3-mercaptobutyrate), a compound represented by the following formula (s-9) (manufactured by Showa Denko Co., Ltd.)

[Formula 74]

EGMP-4: tetraethylene glycol bis(3-mercaptopropionate), a compound represented by the following formula (s-4) (manufactured by Showa Denko Co., Ltd.)

[Formula 75]

TS-G: A compound represented by the following formula (s-11) (manufactured by Shikoku Kasei Kogyo Co., Ltd.)

[Formula 76]

3CTS-G: A compound represented by the following formula (s-12) (manufactured by Shikoku Kasei Kogyo Co., Ltd.)

[Formula 77]

BTGL: butyl thioglycolate, a compound represented by the following formula (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

[Formula 78]

4-HBA: 4-hydroxybutyl acrylate

HEMA: 2-hydroxyethyl methacrylate

GMA: glycidyl methacrylate

A-TMM-3LM-N: A mixture of the following two compounds, the amount of the compound on the left in the mixture based on gas chromatography measurement is about 57% (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[Formula 79]

A-9550: A mixture of the following two compounds, the amount of the pentacrylate compound on the left in the mixture estimated from the hydroxyl value is about 50% (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), hydroxyl value: 50 mgKOH/g

[Formula 80]

・KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.)

<Synthesis of Raw Polymers>

(Synthesis of raw polymer 1)

Into a reaction vessel equipped with a stirrer and cooling tube and a dropping funnel, 602.56 g of a 75% toluene solution of 2-norbornene (451.92 g in terms of NB, 4.8 mol), maleic anhydride (MA, 470.69 g, 4.8 mol) and methylethyl 2238.50 g of ketones (MEK) were added and stirred and dissolved. Then, after removing dissolved oxygen in the system by nitrogen bubbling, it was heated, and when the internal temperature reached 80 ° C., dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name : A solution of V-601, 44.21 g, 0.19 mol) and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP, 140.73 g, 0.29 mol) in 189.74 g of MEK was added for 1 hour. Then, it was reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. A white solid was precipitated by adding the polymerization solution obtained above dropwise to 3686.4 g of methanol. After further washing the obtained white solid with 3686.4 g of methanol, vacuum drying at a temperature of 120 ° C., a polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride (raw polymer 1 ) to obtain 908.1 g.

As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2700, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.57.

[Structural Analysis of Raw Polymer 1]

Synthesis of the raw material polymer 1 is initiated in a state in which the monomer and PEMP are dissolved in a solvent at the start of the reaction, and then the reaction proceeds to produce a polymer. When each of the reaction solution and the obtained polymer was analyzed, the following results were obtained.

(a) analysis of reaction solution

In the GPC measurement of the reaction solution before re-precipitation purification, no PEMP single peak was observed. That is, it was confirmed that PEMP did not remain in the reaction solution. In addition, in GC (gas chromatography) measurement of the reaction solution before re-precipitation purification, the peaks of 2-norbornene alone and maleic anhydride alone in the reaction solution after the reaction are reduced compared to before the reaction, and 2-norbornene and anhydride It was confirmed that maleic acid reacted and formed a polymer.

Measurement conditions for gas chromatography measurement were as follows.

・GC device: GC-2030 (Shimadzu Seisakusho Co., Ltd.)

・Carrier gas: N2

Detector: Hydrogen salt ionization (FID) detector, FID temperature: 300 ° C

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

Vaporization chamber temperature: 210℃

Column flow rate: 0.64mL/min

Column heating conditions: 50℃ 5min hold, 20℃/min temperature increase to 300℃, 300℃ 10min hold

(b) analysis of the polymer

In the GPC measurement of the polymer after reprecipitation purification, peaks of PEMP alone, 2-norbornene alone, and maleic anhydride alone were not confirmed. That is, it was confirmed that PEMP, 2-norbornene alone, and maleic anhydride did not remain in the polymer.

The amount of sulfur in the raw material polymer 1 synthesized using PEMP was confirmed by elemental analysis by flask burning and ion chromatography, and it was confirmed that elemental sulfur was present in the raw material polymer 1. In addition, in the ¹³ C-NMR measurement of raw material polymer 1, the appearance of a peak b derived from carbon b was confirmed around 62.0 ppm. That is, it was confirmed that PEMP was introduced into the polymer.

(c) In the ¹³ C-NMR measurement of raw material polymer 1, peak a derived from carbon a of PEMP alone represented by the following formula (i) was not confirmed, and instead, thioe of raw material polymer 1 represented by the following formula (ii) A peak c from carbon c corresponding to the terminator (RS-R') appeared. The integral value of this peak c was approximately twice the integral value of peak b.

[Formula 81]

(By ¹³ C-NMR measurement of the PEMP alone represented by the formula (i), the peak a derived from carbon a was confirmed around 19.0 ppm and the peak b derived from carbon b was confirmed around 62.0 ppm.)

[Formula 82]

(By the ¹³ C-NMR measurement of the raw material polymer 1 represented by formula (ii), the peak c derived from carbon c was confirmed at around 28 ppm.)

From the above (a) and (b), it is understood that the introduced PEMP, 2-norbornene simplex and maleic anhydride reacted and were introduced into the polymer.

Based on this and the experimental results of (c) above, further considering the raw material of the above (synthesis of raw material polymer 1), the molecular structure of raw material polymer 1 is represented by the following general formula (I-1) It can be seen that the structure is provided.

[Formula 83]

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

[Formula 84]

[Formula 85]

The polymers of Examples synthesized using the raw material polymer 1 having the structure also have the same structure.

The conditions of ¹³ C-NMR measurement are as follows.

(Test conditions) A measurement sample was prepared by adding a measurement solvent to a weighed sample to adjust the concentration, and then pouring a prescribed amount into a sample tube for NMR measurement.

・Measurement device: Nihon Denshi JNM-ECA400 superconducting FT-NMR device

Resonance frequency: 100.53MHz

・Measurement core: ¹³ C

・Measurement method: NNE measurement (inverse gate decoupling method)

・Pulse width: 3.83μsec

·Pulse repetition waiting time: 30s

・Number of integrations: 4096 times

・Measurement temperature: room temperature

・Measurement solvent: DMSO-d ₆ (deuterated dimethyl sulfoxide)

Sample concentration: 20% (w/v)

(Synthesis of raw polymer 2)

In an appropriately sized reaction vessel equipped with a stirrer and a cooling tube, 353.02 g (3.6 mol) of maleic anhydride and 338.94 g (3.6 mol) of 2-norbornene were mixed with dimethyl 2,2'-azobis(2-methyl propionate) 41.45 g (0.180 mol) was weighed in. These were dissolved in a mixed solvent composed of 578.98 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution.

With respect to this solution, nitrogen was ventilated for 30 minutes to remove oxygen, and then, by heating at a temperature of 63 ° C. for 9.5 hours while stirring, maleic anhydride and 2-norbornene were polymerized to prepare a polymerization solution.

After diluting the polymerization solution obtained above with 712.92 g of methyl ethyl ketone, it was added dropwise to 8519.9 g of methanol to precipitate a white solid. By vacuum-drying the obtained white solid at a temperature of 120 degreeC, 550.4 g of polymers (raw polymer 2) provided with the structural unit derived from 2-norbornene and the structural unit derived from maleic anhydride were obtained.

As a result of GPC measurement of the obtained polymer, 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.

(Synthesis of raw polymer 3)

In an appropriately sized reaction vessel equipped with a stirrer and a cooling tube, 353.02 g (3.6 mol) of maleic anhydride and 338.94 g (3.6 mol) of 2-norbornene were mixed with dimethyl 2,2'-azobis(2-methyl 33.16 g (0.144 mol) of propionate) were weighed in. These were dissolved in a mixed solvent composed of 1030.1 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution.

This solution was aerated with nitrogen for 30 minutes to remove oxygen, then heated at 65°C for 1.5 hours with stirring, and then further heated at 80°C for 6 hours to obtain maleic anhydride and 2-norbornene. Polymerization was performed to prepare a polymerization solution.

A white solid was precipitated by adding the polymerization solution obtained above dropwise to 8519.9 g of methanol. By vacuum-drying the obtained white solid at a temperature of 120 degreeC, 607.5 g of polymers (raw polymer 3) provided with the structural unit derived from 2-norbornene and the structural unit derived from maleic anhydride were obtained.

As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 7000, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.82.

(Synthesis of raw polymer 4)

In a reaction vessel equipped with a stirrer and cooling tube and a dropping funnel, 602.56 g of a 75% toluene solution of 2-norbornene (451.92 g in terms of 2-norbornene, 4.8 mol), maleic anhydride (MAN, 470.69 g, 4.8 mol) And 2281.74 g of methyl ethyl ketone (MEK) was added, and it stirred and dissolved. Subsequently, dissolved oxygen in the system was removed by nitrogen bubbling, and then heated, and when the internal temperature reached 80°C, dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V- A solution of 601, 44.21 g, 0.19 mol) and PEMP (93.82 g, 0.19 mol) in 193.4 g of MEK was added over 1 hour. Then, it was reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. A white solid was precipitated by adding the polymerization solution obtained above dropwise to 3686.4 g of methanol. The obtained white solid was further washed with 3686.4 g of methanol and then vacuum dried at a temperature of 120 ° C. to obtain a polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride (raw polymer 4 ) to obtain 910.1 g.

As a result of measuring the obtained raw material polymer 4 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3500, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.62.

The amount of sulfur in the obtained polymer was confirmed by elemental analysis by flask burning and ion chromatography, and it was confirmed that elemental sulfur was present in the polymer.

In the GPC measurement of the reaction solution, no peak of PEMP alone was confirmed and no unreacted PEMP remained, confirming that PEMP had been introduced into the raw material polymer 4.

In addition, by ¹³ C-NMR measurement of the raw material polymer 4, it was confirmed that PEMP was introduced into the raw material polymer 4.

As a result of elemental analysis, the sulfur content in the starting polymer 4 was 2.4 wt%.

(Synthesis of raw polymer 5)

A polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride in the same manner as in the raw material polymer 4 except that TMMP (101.99 g, 0.25 mol) was used instead of PEMP (raw material Polymer 5) 900.1 g was obtained.

As a result of measuring the obtained raw material polymer 5 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,100, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.74.

In the GPC measurement of the reaction solution, no peak of TMMP alone was confirmed and no unreacted TMMP remained, confirming that TMMP had been introduced into the raw material polymer 5.

In addition, by ¹³ C-NMR measurement of the raw material polymer 5, it was confirmed that TMMP was introduced into the raw material polymer 5.

The amount of sulfur in the obtained polymer was confirmed by elemental analysis by flask burning and ion chromatography, and it was confirmed that elemental sulfur was present in the polymer.

(Synthesis of raw polymer 6)

A polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride in the same manner as in the raw material polymer 4 except that DPMP (100.23 g, 0.13 mol) was used instead of PEMP (raw material Polymer 6) 890.2 g was obtained.

As a result of measuring the obtained raw material polymer 6 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,600, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 2.02.

In the GPC measurement of the reaction solution, no peak of DPMP alone was confirmed and no unreacted DPMP remained, confirming that DPMP was introduced into the raw material polymer 6.

In addition, by ¹³ C-NMR measurement of raw material polymer 6, it was confirmed that DPMP was introduced into raw material polymer 6.

The amount of sulfur in the obtained polymer was confirmed by elemental analysis by flask burning and ion chromatography, and it was confirmed that elemental sulfur was present in the polymer.

(Synthesis of raw polymer 7)

A polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride (raw material Polymer 7) 879.9 g was obtained.

As a result of measuring the obtained raw material polymer 7 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,900, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 2.30.

In the GPC measurement of the reaction solution, no peak of TEMPIC alone was confirmed, and no unreacted TEMPIC remained. Therefore, it was confirmed that TEMPIC was introduced into the raw material polymer 7.

In addition, by ¹³ C-NMR measurement of raw material polymer 7, it was confirmed that TEMPIC was introduced into raw material polymer 7.

The amount of sulfur in the obtained polymer was confirmed by elemental analysis by flask burning and ion chromatography, and it was confirmed that elemental sulfur was present in the polymer.

(Synthesis of raw polymer 8)

In a reaction vessel equipped with a stirrer and a cooling tube and a dropping funnel, 50.21 g of a 75% toluene solution of 2-norbornene (37.66 g in terms of 2-norbornene, 0.400 mol), maleic anhydride (MAN, 39.22 g, 0.400 mol) And 189.32 g of methyl ethyl ketone (MEK) was added, and it stirred and dissolved. Subsequently, dissolved oxygen in the system was removed by nitrogen bubbling, and then heated, and when the internal temperature reached 80°C, dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V- 601, 3.68 g, 0.016 mol) and Karenz MT (registered trademark) PE1 (8.72 g, 0.016 mol) in 15.75 g of MEK were added for 1 hour. Then, it was reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. A white solid was precipitated by adding the polymerization solution obtained above dropwise to 1228.8 g of methanol. The obtained white solid was further washed with 307.2 g of methanol and then vacuum dried at a temperature of 120 ° C. to obtain a polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride (raw polymer 8 ) to obtain 64.5 g. As a result of measuring the obtained raw material polymer 8 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,800, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.45.

In the GPC measurement of the reaction solution, the peak of Karenz MT PE1 alone was not confirmed, and since no unreacted Karenz MT PE1 remained, it was confirmed that Karenz MT PE1 was introduced into the raw material polymer 8.

In addition, by ¹³ C-NMR measurement of the raw material polymer 8, it was confirmed that Karenz MT PE1 was introduced into the raw material polymer 8.

The amount of sulfur in the obtained polymer was confirmed by elemental analysis by flask burning and ion chromatography, and it was confirmed that elemental sulfur was present in the polymer.

(Synthesis of raw polymer 9)

In a reaction vessel equipped with a stirrer and a cooling tube and a dropping funnel, 50.21 g of a 75% toluene solution of 2-norbornene (37.66 g in terms of 2-norbornene, 0.400 mol), maleic anhydride (MAN, 39.22 g, 0.400 mol) And 202.18 g of methyl ethyl ketone (MEK) was added, and it stirred and dissolved. Subsequently, dissolved oxygen in the system was removed by nitrogen bubbling, and then heated, and when the internal temperature reached 80°C, dimethyl 2,2'-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V- A solution of 601, 3.68 g, 0.016 mol) and EGMP-4 (11.90 g, 0.032 mol) in 16.23 g of MEK was added over 1 hour. Then, it was reacted at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. A white solid was precipitated by adding the polymerization solution obtained above dropwise to 1228.8 g of methanol. After further washing the obtained white solid with 307.2 g of methanol, vacuum drying at a temperature of 120 ° C. to obtain a polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride (raw polymer 9 ) to obtain 64.5 g.

As a result of measuring the obtained raw material polymer 9 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,900, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 2.57.

In the GPC measurement of the reaction solution, no peak of EGMP-4 alone was confirmed, and since no unreacted EGMP-4 remained, it was confirmed that EGMP-4 was introduced into the raw material polymer 9.

In addition, by ¹³ C-NMR measurement of the raw material polymer 9, it was confirmed that EGMP-4 was introduced into the raw material polymer 9.

The amount of sulfur in the obtained polymer was confirmed by elemental analysis by flask burning and ion chromatography, and it was confirmed that elemental sulfur was present in the polymer.

(Synthesis of raw polymer 10)

A polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride in the same manner as in the raw material polymer 4, except that TS-G (73.45 g, 0.19 mol) was used instead of PEMP. (Raw polymer 10) 860.23 g was obtained.

As a result of measuring the obtained raw material polymer 10 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,300, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.65.

In the GPC measurement of the reaction solution, no peak of TS-G alone was observed and no unreacted TS-G remained, confirming that TS-G had been introduced into the raw material polymer 10.

In addition, by ¹³ C-NMR measurement of the raw material polymer 10, it was confirmed that TS-G was introduced into the raw material polymer 10.

The amount of sulfur in the obtained polymer was confirmed by elemental analysis by flask burning and ion chromatography, and it was confirmed that elemental sulfur was present in the polymer.

(Synthesis of raw polymer 11)

A polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride in the same manner as in the raw material polymer 4, except that 3CTS-G (84.23 g, 0.19 mol) was used instead of PEMP (Raw polymer 11) 900.1 g was obtained.

As a result of measuring the obtained raw material polymer 11 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3100, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.61.

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

In addition, by ¹³ C-NMR measurement of the raw material polymer 11, it was confirmed that 3CTS-G was introduced into the raw material polymer 11.

The amount of sulfur in the obtained polymer was confirmed by elemental analysis by flask burning and ion chromatography, and it was confirmed that elemental sulfur was present in the polymer.

(Synthesis of raw polymer 12)

A polymer having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride (raw material 867.1 g of Polymer 12) was obtained.

As a result of measuring the obtained raw material polymer 12 using gel permeation chromatography (GPC), the weight average molecular weight Mw was 2,900, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 2.57.

In the GPC measurement of the reaction solution, no peak of BTGL alone was observed and no unreacted BTGL remained, confirming that BTGL had been introduced into the raw material polymer 12.

In addition, by ¹³ C-NMR measurement of the raw material polymer 12, it was confirmed that BTGL was introduced into the raw material polymer 12.

The amount of sulfur in the obtained polymer was confirmed by elemental analysis by flask burning and ion chromatography, and it was confirmed that elemental sulfur was present in the polymer.

[Example 1]

(Synthesis of polymers)

The MA unit of the raw material polymer 1 is ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), followed by an epoxy group-containing (meth)acrylic compound ( Polymer P1 obtained by reacting with GMA) was produced. Details will be described below.

First, 100.54 g of MEK was added to 60 g of raw material polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. Further, 40.51 g (0.281 mol) of 4-HBA was added thereafter and reacted at a temperature of 70°C for 4 hours. Further, after that, 26.62 g (0.187 mol) of GMA was added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. After that, the polymer was purified in the following procedure.

The polymer was reprecipitated with an excess of toluene.

• The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of toluene was repeated twice.

• The operation of washing the polymer powder after washing twice with excess water was performed three times.

- The obtained reaction product was dried at 40 degreeC for 16 hours.

By the above, the structural unit derived from maleic anhydride in a raw material polymer was ring-opened with A-TMM-3LM-N and 4-HBA, and polymer P1 made to react with GMA was obtained.

By GPC measurement of the polymer P1, peak disappearance of the polyfunctional (meth)acrylic compound, monofunctional (meth)acrylic compound, and epoxy group-containing (meth)acrylic compound was confirmed. Thus, it was confirmed that the obtained polymer P1 did not contain an unreacted (meth)acrylic compound, a (meth)acrylic compound having no hydroxyl group, or an unreacted epoxy group-containing (meth)acrylic compound.

In Table 1, the components used in the Synthesis Example and the introduced amount of each component are shown in terms of maleic anhydride (MA), and the amount of each structural unit (mol fraction, mol%) is calculated by ¹ H-NMR integral value analysis, It was expressed in terms of maleic anhydride (MA).

Fig. 2 shows a ¹ H-NMR chart of polymer P1, and Fig. 3 shows a partially enlarged peak around 6.0 ppm.

In addition to the peak corresponding to 3H of the acryloyl group (-CH=CH ₂ ) of 5.8-6.7 ppm shown in the ¹ H-NMR chart of polymer P1 of FIG. 3, 5.6-5.8 ppm and 6.0- A peak corresponding to the methacryloyl group (-C(CH ₃ )=CH ₂ of 2H (-C(CH ₃ )=CH ₂ of CH ₂ ) appeared at 6.1 ppm. In the GPC measurement of polymer P1, Since the peaks of the trifunctional (meth)acrylic compound (A-TMM-3LM-N), monofunctional (meth)acrylic compound (4-HBA), and epoxy group-containing (meth)acrylic compound (GMA) in the reaction are not visible, It is understood that an acryloyl group and a methacryloyl group derived from GMA were introduced into the polymer.

In addition, in the GPC measurement of the reaction solution before and after the ring-opening reaction and before and after the GMA addition reaction, the peak derived from the trifunctional (meth)acrylic compound (A-TMM-3LM-N) decreases before and after the ring-opening reaction, and before and after the GMA addition reaction. Also from the fact that the peak derived from GMA decreased, it is understood that A-TMM-3LM-N and GMA were introduced into the polymer.

(Preparation of polymer solution)

100 parts by mass of the obtained polymer P1 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution 1 having a solid content concentration of 30% by mass.

(Preparation of photosensitive resin composition)

The photosensitive resin composition 1 was prepared by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid concentration was 30% by mass.

Solid content in polymer solution 1 (polymer P1): 100 parts by mass

- Polyfunctional acrylate (dipentaerythritol hexaacrylate) (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by mass

Photopolymerization initiator (manufactured by BASF, Irgacure OXE01): 5 parts by mass

Adhesion aid (Shin-Etsu Chemical Industry Co., Ltd., KBM-403): 1 part by mass

・Surfactant (manufactured by DIC Corporation, F-556): 0.5 parts by mass

The obtained photosensitive resin composition was filtered with a PTFE membrane filter Millex-LS (manufactured by Merck Millipore Co., Ltd.) as necessary to remove insoluble matter.

[Example 2]

Polymer P2 was prepared in the same manner as in Example 1 except that the addition amount of 4-HBA was changed to 54.02 g, GMA to 33.28 g, and MEK to 100.91 g. Polymer solution 2 containing polymer P2 in the same manner as in Example 1 prepared The photosensitive resin composition was prepared similarly to Example 1.

[Example 3]

Polymer P3 was produced in the same manner as in Example 1, except that the addition amount of 4-HBA was changed to 56.27 g and MEK was changed to 100.14 g, and polymer solution 3 containing polymer P3 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 4]

Polymer P4 was produced in the same manner as in Example 1 except that the addition amount of 4-HBA was changed to 27.01 g and MEK was changed to 102.93 g, and polymer solution 4 containing polymer P4 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 5]

Polymer P5 was prepared in the same manner as in Example 1 except that the addition amount of 4-HBA was changed to 56.27 g, GMA to 39.94 g, and MEK to 101.01 g. Polymer solution 5 containing polymer P5 in the same manner as in Example 1 prepared The photosensitive resin composition was prepared similarly to Example 1.

[Example 6]

(Synthesis of polymers)

Polymer P6 obtained by ring-opening the MA unit of raw material polymer 1 with a monofunctional (meth)acrylic compound (HEMA) and then reacting with an epoxy group-containing (meth)acrylic compound (GMA) was produced. Details will be described below.

First, 112.76 g of MEK was added to 60 g of raw material polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 25.38 g (0.195 mol) of HEMA was added to this solution, and then 6.00 g (0.059 mol) of triethylamine was added and reacted at a temperature of 70°C for 6 hours. Further, after that, 26.62 g (0.187 mol) of GMA was added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. After that, the polymer was purified in the following procedure.

• The polymer was re-precipitated with an excess of water.

• The operation of washing the polymer powder obtained by reprecipitation with an excess amount of water was repeated twice.

- The obtained reaction product was dried at 40 degreeC for 16 hours.

By the above, the structural unit derived from maleic anhydride in a raw material polymer was ring-opened with HEMA, and polymer P6 made to react with GMA was obtained.

Disappearance of the peak of the monofunctional (meth)acrylic compound used and the peak of the epoxy group-containing (meth)acrylic compound was confirmed by GPC measurement of polymer P6. Thus, it was confirmed that neither an unreacted (meth)acrylic compound nor an epoxy group-containing (meth)acrylic compound was contained in the obtained polymer P6.

In Table 1, the components used in the Synthesis Example and the introduced amount of each component are shown in terms of maleic anhydride (MA), and the amount of each structural unit (mol fraction, mol%) is calculated by ¹ H-NMR integral value analysis, It was expressed in terms of maleic anhydride (MA).

¹ H-NMR measurement confirmed that polymer P6 had a structure in which HEMA was ring-opened and a structure in which GMA reacted.

Polymer solution 6 containing polymer P6 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 7]

100 parts by mass of Polymer P1 obtained in Example 1 and 5 parts by mass of KBM-803 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution 7 having a solid content concentration of 30% by mass. The photosensitive resin composition was prepared similarly to Example 1.

[Example 8]

100 parts by mass of Polymer P2 obtained in Example 2 and 5 parts by mass of KBM-803 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution 8 having a solid content concentration of 30% by mass. The photosensitive resin composition was prepared similarly to Example 1.

[Example 9]

100 parts by mass of Polymer P3 obtained in Example 3 and 5 parts by mass of KBM-803 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution 9 having a solid content concentration of 30% by mass. The photosensitive resin composition was prepared similarly to Example 1.

[Example 10]

100 parts by mass of Polymer P4 obtained in Example 4 and 5 parts by mass of KBM-803 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution 10 having a solid content concentration of 30% by mass. The photosensitive resin composition was prepared similarly to Example 1.

[Example 11]

100 parts by mass of Polymer P5 obtained in Example 5 and 5 parts by mass of KBM-803 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution 11 having a solid content concentration of 30% by mass. The photosensitive resin composition was prepared similarly to Example 1.

[Example 12]

(Synthesis of polymers)

Polymer P10 obtained by ring-opening the MA unit of raw material polymer 1 with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and then reacting with an epoxy group-containing (meth)acrylic compound (GMA) was produced. Details will be described below.

First, 100.57 g of MEK was added to 60 g of raw material polymer 1 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. Furthermore, after that, 13.31 g (0.094 mol) of GMA was added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. After that, the polymer was purified in the following procedure.

The polymer was reprecipitated with an excess of toluene.

• The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of toluene was repeated twice.

• The operation of washing the polymer powder after washing twice with excess water was performed three times.

- The obtained reaction product was dried at 40 degreeC for 16 hours.

By the above, the structural unit derived from maleic anhydride in a raw material polymer was ring-opened with A-TMM-3LM-N, and polymer P10 made to react with GMA was obtained.

By GPC measurement of the polymer P10, peak disappearance of the polyfunctional (meth)acrylic compound used and the epoxy group-containing (meth)acrylic compound was confirmed. Thus, it was confirmed that the obtained polymer P10 did not contain unreacted (meth)acrylic compounds, hydroxyl-free (meth)acrylic compounds, and unreacted epoxy-group-containing (meth)acrylic compounds.

¹ H-NMR measurement confirmed that polymer P10 had a structure in which A-TMM-3LM-N was ring-opened and a structure in which GMA reacted.

Polymer solution 12 containing polymer P10 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 13]

(Synthesis of polymers)

The MA unit of raw material polymer 4 is ring-opened with a pentafunctional (meth)acrylic compound (A-9550) and a monofunctional (meth)acrylic compound (4-HBA), followed by reaction with an epoxy group-containing (meth)acrylic compound (GMA). The resulting polymer P12 was produced. Details will be described below.

First, 100.57 g of MEK was added to 60 g of raw material polymer 4 (0.312 mol in terms of MA) to prepare a solution. Next, 70.06 g of A-9550 was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. Further, 56.27 g (0.390 mol) of 4-HBA was added thereafter and reacted at a temperature of 70°C for 4 hours. Further, after that, 26.62 g (0.187 mol) of GMA was added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. After that, the polymer was purified in the following procedure.

The polymer was reprecipitated with an excess of toluene.

• The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of toluene was repeated twice.

• The operation of washing the polymer powder after washing twice with excess water was performed three times.

- The obtained reaction product was dried at 40 degreeC for 16 hours.

By the above, the structural unit derived from maleic anhydride in a raw material polymer was ring-opened with A-9550 and 4-HBA, and polymer P12 made to react with GMA was obtained.

By GPC measurement of the polymer P12, peak disappearance of the polyfunctional (meth)acrylic compound, the monofunctional (meth)acrylic compound, and the epoxy group-containing (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P12 did not contain an unreacted (meth)acrylic compound, a (meth)acrylic compound having no hydroxyl group, or an unreacted epoxy group-containing (meth)acrylic compound.

In Table 1, the components used in the Synthesis Example and the introduced amount of each component are shown in terms of maleic anhydride (MA), and the amount of each structural unit (mol fraction, mol%) is calculated by ¹ H-NMR integral value analysis, It was expressed in terms of maleic anhydride (MA).

¹ H-NMR measurement confirmed that polymer P12 had a structure in which A-9550 and 4-HBA were ring-opened, and a structure in which GMA reacted.

Polymer solution 13 containing polymer P12 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 14]

(Synthesis of polymers)

The MA unit of the raw material polymer 4 is ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N), further ring-opened by reaction with water, and then an epoxy group-containing (meth)acrylic compound (GMA) Polymer P13 obtained by reacting with was produced. Details will be described below.

First, 100.57 g of MEK was added to 60 g of raw material polymer 4 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. Further, after that, 0.90 g (0.050 mol) of water was added and reacted at a temperature of 70°C for 2 hours. Further, after that, 26.62 g (0.187 mol) of GMA was added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. After that, the polymer was purified in the following procedure.

The polymer was reprecipitated with an excess of toluene.

• The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of toluene was repeated twice.

• The operation of washing the polymer powder after washing twice with excess water was performed three times.

- The obtained reaction product was dried at 40 degreeC for 16 hours.

By the above, the structural unit derived from maleic anhydride in a raw material polymer was ring-opened with A-TMM-3LM-N and water, and polymer P13 made to react with GMA was obtained.

By GPC measurement of the polymer P13, peak disappearance of the polyfunctional (meth)acrylic compound used and the epoxy group-containing (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P13 did not contain an unreacted (meth)acrylic compound, a (meth)acrylic compound having no hydroxyl group, or an unreacted epoxy group-containing (meth)acrylic compound.

In Table 1, the components used in the Synthesis Example and the introduced amount of each component are shown in terms of maleic anhydride (MA), and the amount of each structural unit (mol fraction, mol%) is calculated by ¹ H-NMR integral value analysis, It was expressed in terms of maleic anhydride (MA).

¹ H-NMR measurement confirmed that polymer P13 had a structure in which A-TMM-3LM-N and water were ring-opened, and a structure in which GMA reacted.

Polymer solution 14 containing polymer P13 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 15]

(Synthesis of polymers)

The MA unit of the raw material polymer 4 is ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N), followed by reaction with an epoxy group-containing (meth)acrylic compound (GMA) to prepare a polymer, and further MA Polymer P14 obtained by ring-opening the unit by reaction with water was produced. Details will be described below.

First, 99.23 g of MEK was added to 60 g of raw material polymer 4 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. Further, after that, 19.97 g (0.140 mol) of GMA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution.

The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. After that, the polymer was purified in the following procedure.

The polymer was reprecipitated with an excess of toluene.

• The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of toluene was repeated twice.

• The operation of washing the polymer powder after washing twice with excess water was performed three times.

- The obtained reaction product was dried at 40 degreeC for 16 hours.

Next, the polymer was dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution having a solid content concentration of 30% by mass. To this polymer solution, 30% by mass of water relative to the polymer solid content was added, and the mixture was reacted at 70°C for 5 hours. The solution after the reaction was subsequently subjected to solvent substitution in the following procedure.

- Solvent replacement: PGMEA was added so that the solid content concentration of the obtained reaction mixture would be 18 mass %, and it mixed until it became uniform. Thereafter, the solvent was removed at 50°C under reduced pressure using a rotary evaporator. It was confirmed that the solid content concentration of the polymer solution reached 27 ± 2% by mass as measured by a heat-drying moisture meter, and the solvent removal operation was stopped. In the same operation, PGMEA was added so that the solid content concentration was 18% by mass, mixed until uniform, and then the solvent was removed at 50 ° C. under reduced pressure to obtain a solid content concentration of 27 ± 2 as measured by a heat-drying moisture meter. The operation of adjusting by mass% was repeated twice more. After that, the solvent was removed or PGMEA was added so that the solid content concentration was 30 ± 3% by mass, and stirring was performed until it became uniform. Water used in the reaction is removed by the above operation, and the solvent is replaced with PGMEA.

In accordance with the above, a structural unit derived from maleic anhydride in the raw material polymer is ring-opened to A-TMM-3LM-N, reacted with GMA, and polymer P14 containing a ring-opened MA unit by reaction with water. A polymer solution 15 was obtained.

By GPC measurement of the polymer P14, peak disappearance of the polyfunctional (meth)acrylic compound and the epoxy group-containing (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P14 did not contain an unreacted (meth)acrylic compound, a (meth)acrylic compound having no hydroxyl group, or an unreacted epoxy group-containing (meth)acrylic compound.

The photosensitive resin composition was prepared similarly to Example 1.

[Example 16]

(Synthesis of polymers)

In the same manner as in Example 3, except that raw polymer 5 was used instead of raw polymer 1, the MA unit of raw material polymer 5 was mixed with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (meth). ) Polymer P15 obtained by ring-opening with an acrylic compound (4-HBA) and then reacting with an epoxy group-containing (meth)acrylic compound (GMA) was produced.

Polymer solution 16 containing polymer P15 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 17]

(Synthesis of polymers)

In the same manner as in Example 3 except for using raw polymer 6 instead of raw polymer 1, the MA unit of raw material polymer 6 was prepared by adding a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (meth). ) Polymer P16 obtained by ring-opening with an acrylic compound (4-HBA) and then reacting with an epoxy group-containing (meth)acrylic compound (GMA) was produced.

Polymer solution 17 containing polymer P16 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 18]

(Synthesis of polymers)

In the same manner as in Example 3 except for using raw polymer 7 instead of raw polymer 1, the MA unit of raw material polymer 7 was prepared by adding a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (meth). ) Polymer P17 obtained by ring-opening with an acrylic compound (4-HBA) and then reacting with an epoxy group-containing (meth)acrylic compound (GMA) was produced.

Polymer solution 18 containing polymer P17 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 19]

(Synthesis of polymers)

In the same manner as in Example 3 except for using the starting polymer 8 instead of the starting polymer 1, the MA unit of the starting polymer 8 was prepared by adding a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (meth). ) Polymer P18 obtained by ring-opening with an acrylic compound (4-HBA) and then reacting with an epoxy group-containing (meth)acrylic compound (GMA) was produced. Polymer solution 19 containing polymer P18 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 20]

(Synthesis of polymers)

In the same manner as in Example 3 except for using raw polymer 9 instead of raw polymer 1, the MA unit of raw material polymer 9 was prepared by adding a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (meth). ) Polymer P19 obtained by ring-opening with an acrylic compound (4-HBA) and then reacting with an epoxy group-containing (meth)acrylic compound (GMA) was produced.

Polymer solution 20 containing polymer P19 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 21]

(Synthesis of polymers)

In the same manner as in Example 3 except for using raw polymer 10 instead of raw polymer 1, the MA unit of raw material polymer 10 was prepared by adding a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (meth). ) Polymer P20 obtained by ring-opening with an acrylic compound (4-HBA) and then reacting with an epoxy group-containing (meth)acrylic compound (GMA) was produced.

Polymer solution 21 containing polymer P20 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Example 22]

(Synthesis of polymers)

In the same manner as in Example 3 except for using raw polymer 11 instead of raw polymer 1, the MA unit of raw material polymer 11 was prepared by adding a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (meth). ) Polymer P21 obtained by ring-opening with an acrylic compound (4-HBA) and then reacting with an epoxy group-containing (meth)acrylic compound (GMA) was produced.

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

[Comparative Example 1]

(Synthesis of polymers)

The MA unit of the raw material polymer 2 is ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA), followed by an epoxy group-containing (meth)acrylic compound ( Polymer P7 obtained by reacting with GMA) was produced. Details will be described below.

First, 102.93 g of MEK was added to 60 g of the raw material polymer 2 (0.312 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3LM-N was added to this solution, and then 18.00 g (0.178 mol) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. Further, 27.12 g (0.187 mol) of 4-HBA was added thereafter and reacted at a temperature of 70°C for 4 hours. Further, after that, 26.62 g (0.187 mol) of GMA was added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. After that, the polymer was purified in the following procedure.

The polymer was reprecipitated with an excess of toluene.

• The operation of washing the polymer powder obtained by reprecipitation with an excessive amount of toluene was repeated twice.

• The operation of washing the polymer powder after washing twice with excess water was performed three times.

- The obtained reaction product was dried at 40 degreeC for 16 hours.

By the above, the structural unit derived from maleic anhydride in a raw material polymer was ring-opened with A-TMM-3LM-N and 4-HBA, and polymer P7 made to react with GMA was obtained.

By GPC measurement of Polymer P7, peak disappearance of the used multifunctional (meth)acrylic compound, monofunctional (meth)acrylic compound, and epoxy group-containing (meth)acrylic compound was confirmed. Thereby, it was confirmed that the obtained polymer P7 did not contain unreacted (meth)acrylic compounds, (meth)acrylic compounds having no hydroxyl groups, and unreacted epoxy-group-containing (meth)acrylic compounds.

In Table 1, the components used in the Synthesis Example and the introduced amount of each component are shown in terms of maleic anhydride (MA), and the amount of each structural unit (mol fraction, mol%) is calculated by ¹ H-NMR integral value analysis, It was expressed in terms of maleic anhydride (MA).

In addition, in the GPC measurement of the reaction solution before and after the ring-opening reaction and before and after the GMA addition reaction, the peak derived from the trifunctional (meth)acrylic compound (A-TMM-3LM-N) decreases before and after the ring-opening reaction, and before and after the GMA addition reaction. Also from the fact that the peak derived from GMA decreased, it is understood that A-TMM-3LM-N and GMA were introduced into the polymer.

Polymer solution 23 containing polymer P7 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Comparative Example 2]

Polymer P8 was prepared in the same manner as in Comparative Example 1, except that the addition amount of 4-HBA was changed to 13.50 g, GMA to 13.31 g, and MEK to 100.80 g. Polymer solution 24 containing polymer P8 in the same manner as in Example 1 prepared The photosensitive resin composition was prepared similarly to Example 1.

[Comparative Example 3]

(Synthesis of polymers)

The MA unit of the raw material polymer 2 was ring-opened with a monofunctional (meth)acrylic compound (HEMA), and then reacted with an epoxy group-containing (meth)acrylic compound (GMA) to produce polymer P9 obtained. Details will be described below.

First, 111.43 g of MEK was added to 60 g of the raw material polymer 2 (0.312 mol in terms of MA) to prepare a solution. Next, 25.38 g (0.195 mol) of HEMA was added to this solution, and then 6.00 g (0.059 mol) of triethylamine was added and reacted at a temperature of 70°C for 6 hours. Furthermore, after that, 13.31 g (0.094 mol) of GMA was added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

The prepared reaction solution was diluted with MEK and treated with an aqueous solution of formic acid to remove the aqueous phase from the reaction solution. After that, the polymer was purified in the following procedure.

• The polymer was re-precipitated with an excess of water.

• The operation of washing the polymer powder obtained by reprecipitation with an excess amount of water was repeated twice.

- The obtained reaction product was dried at 40 degreeC for 16 hours.

By the above, the structural unit derived from maleic anhydride in a raw material polymer was ring-opened with HEMA, and polymer P9 made to react with GMA was obtained.

Disappearance of the peak of the monofunctional (meth)acrylic compound used and the peak of the epoxy group-containing (meth)acrylic compound was confirmed by GPC measurement of polymer P9. Thus, it was confirmed that the obtained polymer P9 did not contain either an unreacted (meth)acrylic compound or an epoxy group-containing (meth)acrylic compound.

In Table 1, the components used in the Synthesis Example and the introduced amount of each component are shown in terms of maleic anhydride (MA), and the amount of each structural unit (mol fraction, mol%) is calculated by ¹ H-NMR integral value analysis, It was expressed in terms of maleic anhydride (MA).

¹ H-NMR measurement confirmed that polymer P9 had a structure in which HEMA was ring-opened and a structure in which GMA reacted.

Polymer solution 25 containing polymer P9 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

[Comparative Example 4]

(Synthesis of polymers)

Polymer solution 26 containing polymer P11 was prepared in the same manner as in Example 12, except that starting polymer 3 was used instead of starting polymer 1. The photosensitive resin composition was prepared similarly to Example 1.

[Comparative Example 5]

(Synthesis of polymers)

In the same manner as in Example 3, except that raw polymer 12 was used instead of raw polymer 1, the MA unit of raw material polymer 12 was mixed with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (meth). ) Polymer P22 obtained by ring opening with an acrylic compound (4-HBA) and then reacting with an epoxy group-containing (meth)acrylic compound (GMA) was produced.

Polymer solution 27 containing polymer P22 was prepared in the same manner as in Example 1. The photosensitive resin composition was prepared similarly to Example 1.

<Evaluation method>

The polymers, polymer solutions, and photosensitive resin compositions synthesized in Examples and Comparative Examples were evaluated according to the following. A result is shown to Tables 1-3.

(Weight average molecular weight (Mw), molecular weight distribution (PDI))

For the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (PDI: Mw/Mn), polystyrene conversion values obtained from a calibration curve of standard polystyrene (PS) obtained by GPC measurement are used. Measurement conditions are as follows. The results are shown in Table 1.

Tosoh Gel Permeation Chromatography Apparatus HLC-8320GPC

Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation

Detector: RI detector for liquid chromatograms

Measurement temperature: 40℃

Solvent: THF

Sample concentration: 2.0 mg/milliliter

(Evaluation of developability (dissolution rate of polymer (or photosensitive resin composition) in alkaline developer))

A resin film having a film thickness of 2 μm ± 0.2 was prepared by spin-coating the polymer solution (or photosensitive resin composition) obtained in Examples and Comparative Examples on a wafer, drying PGMEA, and prebaking at a temperature of 100 ° C. for 2 minutes.

Each wafer of this resin film was immersed in a 2.38 mass% TMAH aqueous solution at a temperature of 23°C, and the dissolution rate of the resin film was measured.

The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film was dissolved and the interference pattern was no longer visible, and dividing the film thickness by the time. A result is shown to Tables 1-3. About a polymer solution, if the alkali dissolution rate is 200 nm/s or more and 2000 nm/s or less, it can be considered that developability is favorable. About the photosensitive resin composition, if the alkali dissolution rate is 200 nm/s or more and 2500 nm/s or less, it can be considered that developability is favorable.

[Evaluation of sensitivity of photosensitive resin composition (2.38% by mass TMAH aqueous solution)]

(Exposure amount at which the remaining film rate is 90% or more)

The photosensitive resin composition obtained in Examples and Comparative Examples was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film with a thickness of about 3.0 μm (±0.3 μm). got an A.

A g+h+i line was applied to this thin film A at an exposure amount of 100 mJ/cm ² with a g+h+i line mask aligner (PLA-501F) manufactured by Canon Inc. was exposed.

After exposure, the thin film was developed with a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 23° C. for the developing time shown in Tables 2 and 3 (immersion per wafer), and exposure at an exposure amount of 1 to 100 mJ/cm ² , to obtain a developed thin film B.

From the film thickness of thin film A and thin film B obtained by the said method, the remaining-film rate was computed from the following formula.

Remaining film rate (%) = (film thickness of thin film B / film thickness of thin film A at each exposure amount) × 100

And the exposure amount used as 90% or more of remaining film rates was made into the sensitivity of each photosensitive resin composition. The results are shown in Tables 2 and 3. If the exposure amount at which the remaining film rate is 90% or more is 50 mJ/cm ² or less, it can be used as a photosensitive composition without any problem, if it is 20 mJ/cm ² or less, the sensitivity is good, and if it is 10 mJ/cm ² or less, the sensitivity is considered particularly excellent. can do.

[Yellow Index]

The photosensitive resin composition was spin-coated on Eagle XG glass (made by Corning, thickness 0.5 mm), and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film with a thickness of about 3.0 μm (±0.1 μm).

The thin film was exposed to a g+h+i line at an exposure amount of 100 mJ/cm ² using a g+h+i line mask aligner (PLA-600F) manufactured by Canon Inc.

After exposure, the thin film was developed with a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (each wafer was immersed) to obtain an exposed and developed thin film at an exposure amount of 100 mJ/cm ² .

The thin film was subjected to heat treatment at 230°C for 30 minutes in air. After cooling the thin film under air at room temperature, the thin film was again subjected to heat treatment at 230°C for 30 minutes under air. The same operation was repeated and the heat treatment was performed 3 times in total for 30 minutes under air.

The yellow index (YI) of the thin film obtained by the above method was measured three times at different measurement locations using a color difference meter CR-5 (manufactured by Konica Minolta), and the average value was taken as the value of YI. The measurement type was transmission measurement, and 100% calibration used uncoated Eagle XG glass (manufactured by Corning, thickness 0.5 mm). The results are shown in Tables 2 and 3. If the yellow index is 1.15 or less, it can be used without problems as a photosensitive resin composition, if it is 1.10 or less, heat discoloration resistance can be regarded as good, and if it is 0.8 or less, heat discoloration resistance can be regarded as particularly good.

[Adhesion during development]

(Adhesion to line pattern)

The photosensitive resin composition was spin-coated on Eagle XG glass (made by Corning, thickness 0.5 mm), and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film with a thickness of about 3.0 μm (±0.1 μm).

A photomask having a total of five glass portions (exposure portions) in which a glass portion (exposure portion) having a width of 40 μm and a vertical width of 400 μm and a chromium portion (light-shielding portion) having a width of 40 μm and a vertical width of 400 μm are alternately formed on this thin film. Through this, the g+h+i line was exposed at an exposure amount of 18 mJ/cm ² with a g+h+i line mask aligner (PLA-501F) manufactured by Canon Inc. By this exposure, since the glass portion of the photomask transmits light, it is exposed at a specified exposure amount, and since the chromium portion does not transmit light, it becomes an unexposed portion, and a line pattern having alternately exposed and unexposed portions is obtained. After exposure, the thin film was developed with a 0.5% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (each wafer was immersed) to obtain an exposed and developed thin film at an exposure amount of 18 mJ/cm ² . The presence or absence of peeling of the line patterns was observed under a microscope for line patterns having a width of 40 μm and a vertical width of 400 μm at a total of five locations after exposure and development.

(Criteria)

○: The line pattern after development adhered to the substrate, and no peeled portion was observed.

x: The line pattern after development WHEREIN: The location peeled from the board|substrate was confirmed.

(Adhesion to dot pattern)

The photosensitive resin composition was spin-coated on Eagle XG glass (made by Corning, thickness 0.5 mm), and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film with a thickness of about 3.0 μm (±0.1 μm).

Through a photomask having a total of three patterns in this thin film, a glass portion (exposure portion) with a width of 50 μm and a vertical width of 50 μm, and a chromium portion (shade portion) around the glass portion, in total, the g+h+i line made by Canon Corporation is passed through. The g+h+i line was exposed with a mask aligner (PLA-501F) at an exposure amount of 18 mJ/cm ² . By this exposure, since the glass portion of the photomask transmits light, it is exposed at the specified exposure amount, and since the chromium portion does not transmit light, it becomes an unexposed portion, and a dot pattern having an exposure amount of 50 μm in width and 50 μm in height is formed. is obtained After exposure, the thin film was developed with a 0.5% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at 23°C for 10 seconds (each wafer was immersed) to obtain an exposed and developed thin film at an exposure amount of 18 mJ/cm ² . The presence or absence of peeling of the line pattern was observed under a microscope for dot patterns having a width of 50 μm and a vertical width of 50 μm at three locations in total after exposure and development.

(Criteria)

○: The dot pattern after development adhered to the substrate, and no exfoliated portion was observed.

x: The dot pattern after development WHEREIN: The location peeled from the board|substrate was confirmed.

[Table 1]

[Table 2]

[Table 3]

The polymers synthesized in Examples 1 to 6 and 12 to 22 all have a structure represented by the general formula (P), and have good sensitivity, reduced yellowing, excellent transparency, and better adhesion to substrates and the like. An excellent cured resin product was obtained. Further, the polymers synthesized in Examples 1 to 6 and 12 to 19, in which the thiol group-containing compound introduced into the polymer is a trifunctional or higher-functional thiol group-containing compound and a thiol group-containing compound containing an ester structure, have particularly reduced yellowing. Transparency was excellent. On the other hand, the polymers synthesized in Comparative Examples 1 to 4 without using a thiol group-containing compound and in Comparative Example 5 using a monofunctional thiol group-containing compound yielded cured resin products having low transparency and lower adhesion to substrates, etc. lost.

The polymer solutions of Examples 7 to 11 in which a predetermined coupling agent (a compound having a thiol group and an alkoxy group) was further added to the polymer solutions of Examples 1 to 5 had better sensitivity and reduced yellowing. , and the adhesion to the substrate was more excellent.

<Production of color filter>

With respect to the photosensitive resin composition prepared in Examples 1-22, the coloring photosensitive resin composition which further added an appropriate amount of pigment dispersion liquid NX-061 (made by Dainichi Seika Kogyo Co., Ltd., green) was prepared.

A green color filter was able to be formed by forming this into a film on a substrate and performing exposure, alkali development, or the like.

In addition, a blue or red color filter could be formed using NX-053 (blue), NX-032 (red), etc. manufactured by the company instead of NX-061 as a pigment dispersion.

<Production of the Black Matrix>

With respect to the photosensitive resin composition prepared in Examples 1-22, the black photosensitive resin composition which further added an appropriate amount of carbon black dispersion liquid NX-595 (made by Dainichi Seika Kogyo Co., Ltd.) was prepared.

A black matrix was able to be formed by forming this into a film on a board|substrate, and performing exposure, alkali developing treatment, etc.

This application claims priority based on Japanese Patent Application No. 2020-158807 filed on September 23, 2020 and Japanese Patent Application No. 2020-201731 filed on December 4, 2020, the disclosure of which All of this is invoked here.

10 substrate
11 Black Matrix
12 color filters
13 Shield
14 transparent electrode layer

Claims (30)

A polymer represented by the following general formula (P).
[Formula 1]

(In the general formula (P),
Y is a monovalent to hexavalent organic group of 1 to 30 carbon atoms derived from a bifunctional or higher thiol group-containing compound;
Chain includes a structural unit represented by the following general formula (AE-1) and a structural unit represented by the following general formula (AE-2).)
[Formula 2]

(In formula (AE-1), Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X is an oxygen atom or a substituted Alternatively, it represents an unsubstituted alkylene group having 1 to 4 carbon atoms, and a ring may be formed by bonding the carbon atom of any one of the alkylene group of Q and the alkylene group of X. In general formula (AE-2), R ^A is , It is a group containing one or more (meth)acryloyl groups.
n is an integer of 1-6. A structure other than Chain may be combined with Y.) The method of claim 1,
Wherein the thiol group-containing compound includes a trifunctional or higher thiol group-containing compound. According to claim 1 or claim 2,
The thiol group-containing compound comprises an ester structure, the polymer. The method according to any one of claims 1 to 3,
The chain further comprises a structural unit represented by the following general formula (NB), the polymer.
[Formula 3]

(In general formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2.) The method according to any one of claims 1 to 4,
The polymer in which said Z contains the group represented by the following general formula (1a).
[Formula 4]

(In general formula (1a), R is a hydrogen atom, a methyl group or an ethyl group.) The method according to any one of claims 1 to 5,
The Chain is a polymer containing a structural unit represented by the following general formula (D).
[Formula 5]

(In general formula (D), R ^D is a group containing a polyfunctional (meth)acryloyl group.) The method according to any one of claims 1 to 6,
The polymer in which said R ^A contains at least 1 sort(s) of group containing 2-6 (meth)acryloyl groups. According to any one of claims 1 to 7,
The polymer in which said R ^A contains at least 1 sort(s) of groups represented by the following general formula (1b), (1c), or (1d).
[Formula 6]

(In formula (1b),
k is 2 or 3;
R is a hydrogen atom or a methyl group, and a plurality of R's may be the same or different,
X ¹ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z is -O- or -OCO-, X is an alkylene group having 1 to 6 carbon atoms), and a plurality of X ¹ may be the same or different,
X ¹ 'is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-) is,
X ² is a k+1 valent organic group having 1 to 12 carbon atoms.)
[Formula 7]

(In formula (1c),
k, R, X ¹ and X ² each have the same meaning as R, k, X ¹ and X ² in the above general formula (1b), a plurality of Rs may be the same as or different from each other, and a plurality of X ¹ may be the same as or different from each other,
X ³ is a divalent organic group having 1 to 6 carbon atoms;
X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms;
X ⁶ is a divalent organic group having 1 to 6 carbon atoms.)
[Formula 8]

(In general formula (1d), n is an integer of 2 to 5.) The method according to any one of claims 1 to 8,
The chain is a polymer containing a structural unit represented by the following general formula (S).
[Formula 9]

(In general formula (S), R ^S is a group containing only one (meth)acryloyl group.) The method according to any one of claims 1 to 9,
The chain further comprises a structural unit represented by the following general formula (MA), the polymer.
[Formula 10]

The method according to any one of claims 1 to 10,
The chain further contains at least one member selected from structural units represented by the following general formula (E) and structural units represented by the following general formula (EE).
[Formula 11]

(In general formulas (E) and (EE), Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X is an oxygen atom , represents a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and a ring may be formed by bonding the carbon atom of any one of the alkylene group of Q and the alkylene group of X.
In general formula (EE), Z, Q, and X which exist in plurality may be the same or different, respectively.) According to any one of claims 1 to 11,
The chain further comprises a structural unit represented by the following general formula (M), the polymer.
[Formula 12]

The method of claim 1,
A polymer represented by the following general formula (P1).
[Formula 13]

(In the general formula (P1), p, q and r respectively represent the molar content of A, B and C in the polymer, p+q+r=1, p is greater than 0, and q is 0 and r is greater than or equal to 0. p, q or r may be the same or different for each structural unit in n [ ].
n is an integer of 1 to 6;
X is hydrogen or an organic group having 1 or more and 30 or less carbon atoms;
Y is a monovalent to hexavalent organic group of 1 to 30 carbon atoms derived from a bifunctional or higher thiol group-containing compound;
A contains a structural unit represented by the following general formula (NB),
B contains a structural unit represented by the following general formula (AE),
C contains a divalent structural unit derived from a copolymerizable compound having a double bond;
A plurality of A's, B's, or C's may be the same or different.
Structures other than the polymer chain represented by []n may be bonded to Y.
[Formula 14]

(In general formula (NB), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2.)
[Formula 15]

(In general formula (AE), Z, Q, and X have the same meaning as in general formula (AE-1), and R ^A is a group containing one or more (meth)acryloyl groups.) The method of claim 13,
The divalent structural unit constituting C is a substituted or unsubstituted divalent structural unit derived from at least one compound selected from indene, maleimide, styrene, and norbornadiene. According to claim 13 or claim 14,
The B is at least one kind of structural unit selected from structural units represented by the following general formula (DE) and the above general formula (SE), and, if necessary, the following general formula (D), the following general formula (S), the following A polymer comprising at least one structural unit selected from structural units represented by the general formula (MA), the following general formula (E), the following general formula (EE), and the following general formula (M).
[Formula 16]

(In the general formula (DE), Q, X, and Z have the same meaning as in the general formula (AE-1), and R ^D is a group containing two or more (meth)acryloyl groups.)
[Formula 17]

(In general formula (SE), Q, X, and Z have the same meaning as in general formula (AE-1), and R ^S is a group containing only one (meth)acryloyl group.)
[Formula 18]

(In general formula (D), R ^D is a group containing a polyfunctional (meth)acryloyl group.)
[Formula 19]

(In general formula (S), R ^S is a group containing only one (meth)acryloyl group.)
[Formula 20]

[Formula 21]

(In the general formula (E), Z, Q, and X have the same meaning as in the general formula (AE-1).)
[Formula 22]

(In the general formula (EE), Z, Q, and X have the same meaning as in the general formula (AE-1), and a plurality of Z, Q, and X may be the same or different, respectively.)
[Formula 23]

The method according to any one of claims 1 to 15,
The polymer wherein the bifunctional or higher thiol group-containing compound constituting Y includes at least one compound selected from compounds represented by the following formulas (s-1) to (s-21).
[Formula 24]

The method according to any one of claims 1 to 16,
The difunctional or higher thiol group-containing compound constituting Y is obtained from compounds represented by the following formulas (s-1) to (s-3), (s-5) and (s-8) to (s-10). A polymer comprising at least one selected compound.
[Formula 25]

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 bifunctional or higher thiol group-containing compound,
A polymer precursor is prepared by reacting the obtained raw material polymer with a polyfunctional (meth)acrylic monomer and/or a monofunctional (meth)acrylic monomer in the presence of a basic catalyst,
Next, a polymer obtained by reacting the obtained polymer precursor with an epoxy group-containing (meth)acrylic compound in the presence of a catalyst.
[Formula 26]

(In general formula (NBm), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2.) The method of claim 18
In the raw material polymer, a polymer chain having a structural unit represented by the following general formula (NB) and a structural unit represented by the following general formula (MA) is derived from at least one thiol group among the bifunctional or higher thiol group-containing compounds. A polymer bonded through an ether group.
[Formula 27]

(In the general formula (NB), R ¹ , R ² , R ³ and R ⁴ , a1 have the same meaning as in the general formula (NBm).)
[Formula 28]

The method of claim 19
The polymer precursor has a polymer chain having a structural unit represented by the general formula (NB), a structural unit represented by the following general formula (D), and/or a structural unit represented by the following general formula (S), A polymer bonded through a thioether group derived from at least one thiol group in an all group-containing compound.
[Formula 29]

[Formula 30]

(In general formula (D), R ^D is a group containing two or more (meth)acryloyl groups. In general formula (S), R ^S is a group containing only one (meth)acryloyl group.) The method of claim 20
The polymer has a structural unit represented by the general formula (NB), a structural unit represented by the general formula (D) and/or a structural unit represented by the general formula (S), and a structure represented by the following general formula (DE) A polymer in which polymer chains having units and/or structural units represented by the following general formula (SE) are bonded via a thioether group derived from at least one thiol group among the bifunctional or higher thiol group-containing compounds.
[Formula 31]

(In formula (DE), Z is a group containing one or more (meth)acryloyl groups. Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. X is an oxygen atom, substituted or unsubstituted Represents a substituted alkylene group having 1 to 4 carbon atoms, and a ring may be formed by bonding the carbon atom of any one of the alkylene group of Q and the alkylene group of X. R ^D is containing two or more (meth)acryloyl groups. It is Ki.)
[Formula 32]

(In the general formula (SE), Z, Q, and X have the same meaning as in the general formula (DE). R ^S is a group containing only one (meth)acryloyl group.) The method according to any one of claims 18 to 21,
Before reacting the polymer precursor with the epoxy group-containing (meth)acrylic compound, water is added to the polymer precursor and heated in the presence of a catalyst. The method according to any one of claims 18 to 22,
A polymer obtained by reacting the polymer precursor and the epoxy group-containing (meth)acrylic compound, then adding water to the reactant and heating it. A polymer solution comprising the polymer according to any one of claims 1 to 23. The method of claim 24
A polymer solution further comprising a compound having a thiol group and an alkoxy group or an oligomer thereof. The method of claim 25
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 which may contain one or more atoms selected from O, N, S, P and Si. Polymer solution. According to claim 25 or claim 26,
The polymer solution in which the compound having a thiol group and an alkoxy group includes a compound represented by the following general formula (a).
[Formula 33]

(In the general formula (a), R each 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 R's are alkoxy groups having 1 to 3 carbon atoms.
L represents an m+n valent organic chain which may contain one or more atoms selected from O, N, S, P and Si.
X represents a divalent organic group which may contain a single bond or a carbonyl group, a (thio)ester group or a (thio)amide group.
Q represents a divalent organic group which may contain a single bond or a carbonyl group, a (thio)ester group, or a (thio)amide group.
m:n (molar ratio) is 1:1 to 1:8, and the weight average molecular weight of the compound is 100 to 2000.) The method according to any one of claims 24 to 27,
A polymer solution used in the formation of a color filter or black matrix. The polymer solution according to any one of claims 24 to 28;
A multifunctional (meth)acrylate monomer,
A photosensitive resin composition comprising a photopolymerization initiator. A cured product of the photosensitive resin composition according to claim 29.

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