JP2022165664A - Photosensitive resin composition and cured film - Google Patents

Abstract

To provide a photosensitive resin composition excellent in curability and capable of obtaining cured material excellent in transparency and durability such as solvent resistance.SOLUTION: A photosensitive resin composition contains a polymer containing maleic anhydride and a norbornene derivative, and a polymerization initiator, and a cured film having a thickness of 3 μm obtained by heating at 230°C for 60 minutes satisfies the following properties (a) and (b). (a) The light transmittance at a wavelength of 400 nm and the light transmittance at a wavelength of 550 nm are 95% or more. (b) A film thickness change rate represented by the following formula after immersing in a mixed solvent of monoethanolamine/DMSO=70/30 (weight ratio) at 70°C for 1 minute is 5.0% or less. Formula: [(film thickness after immersion at 70°C for 1 minute - film thickness before immersion)/film thickness before immersion]×100.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition and a cured film.

A liquid crystal display device and a solid-state imaging device usually have a color filter and a black matrix. A photosensitive resin composition is often used for forming a color filter or a black matrix.

For example, in Patent Document 1, at least in the side chain, an alkali-soluble resin having a group having an acidic group and two or more different polymerizable unsaturated groups, a polymerizable compound, and a photosensitive containing a photopolymerization initiator A resin composition is disclosed. In Examples of Document 1, it is described that a 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 colored photosensitive resin composition containing a polymer containing repeating units derived from predetermined norbornene and maleic acid, a photoradical polymerization initiator, and a colorant. In the synthesis example of the literature, it is described that the ring-opening rate (esterification rate) of maleic anhydride was 90%.

Patent Literature 3 discloses a method for producing a polymer including a step of reacting a precursor polymer having ring-opened maleic anhydride sites with a compound having an epoxy group. In the examples of this document, glycidyl methacrylate is described as a compound with an epoxy group.

WO2012/147706 WO2016/194619 WO2017/154439

However, in the conventional techniques described in Patent Documents 1 to 3, there is room for improvement in durability such as transparency and solvent resistance of cured products obtained from photosensitive resin compositions.

The present inventors have found that the above problems can be solved by containing a polymer or the like having a predetermined structure and satisfying predetermined characteristics of a cured film, and have completed the present invention.
That is, the present invention can be shown below.

（一般式（２）中、Ｚは１以上の（メタ）アクリロイル基を含む基である。Ｑは水素原子または置換または未置換の炭素数１～６のアルキル基である。Ｘは酸素原子、置換または未置換の炭素数１～４のアルキレン基を表し、Ｑの前記アルキル基とＸの前記アルキレン基の何れかの炭素原子とが結合して環を形成してもよい。
一般式（３）中、Ｒ^Ａは、１以上の（メタ）アクリロイル基を含む基である。
一般式（５）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子または炭素数１～３０の有機基であり、ａ１は０、１または２である。） According to the invention,
a polymer containing structural units (1) to (5) represented by the following general formulas (1) to (5);
a polymerization initiator;
including
Provided is a photosensitive resin composition in which a cured film having a thickness of 3 μm obtained by heating at 230° C. for 60 minutes satisfies the following properties (a) and (b).
(a) The light transmittance at a wavelength of 400 nm and the light transmittance at a wavelength of 550 nm are 95% or more.
(b) The film thickness change rate represented by the following formula after being immersed in a mixed solvent of monoethanolamine/DMSO=70/30 (weight ratio) at 70° C. for 1 minute is 5.0% or less.
Formula: [(film thickness after immersion at 70 ° C. for 1 minute - film thickness before immersion) / film thickness before immersion] × 100

(In general formula (2), 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, It represents a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and the alkyl group for Q and any carbon atom of the alkylene group for X may combine to form a ring.
In general formula (3), ^RA is a group containing one or more (meth)acryloyl groups.
In general formula (5), 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 invention,
A cured film comprising the photosensitive resin composition is provided.

The photosensitive resin composition of the present invention has excellent curability and can provide a cured product having excellent durability such as transparency and solvent resistance. In other words, it is possible to provide a cured product having an excellent balance of these properties.

1 is a diagram (cross-sectional view) schematically showing an example of the structure of a liquid crystal display device and/or a solid-state imaging device; FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in all the drawings, the same constituent elements are denoted by the same reference numerals, and the description thereof will be omitted as appropriate. Also, all drawings are for illustration purposes only. The shape and dimensional ratio of each member in the drawings do not necessarily correspond to the actual article. In this specification, the notation "a to b" in the description of numerical ranges means from a to b, unless otherwise specified. For example, "5 to 90%" means "5% to 90%".
The notation "(meth)acryl" used herein represents a concept that includes both acryl and methacryl. The same applies to similar notations such as "(meth)acrylate".

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment contains a polymer containing structural units (1) to (5) represented by general formulas (1) to (5), and a polymerization initiator.
A cured film having a thickness of 3 μm obtained by heating the photosensitive resin composition at 230° C. for 60 minutes satisfies the following characteristics (a) and (b).
(a) Light transmittance at a wavelength of 400 nm and light transmittance at a wavelength of 550 nm are 95% or more, preferably 96% or more.
(b) The film thickness change rate represented by the following formula after being immersed in a mixed solvent of monoethanolamine/DMSO=70/30 (weight ratio) at 70° C. for 1 minute is 5.0% or less, preferably 4.5% or less.
Formula: [(film thickness after immersion at 70 ° C. for 1 minute - film thickness before immersion) / film thickness before immersion] × 100

The photosensitive resin composition of the present embodiment is excellent in curability and heat resistance because it contains the structural unit, and further satisfies the properties (a) and (b), so durability such as transparency and solvent resistance It is possible to provide a cured product excellent in

The cured product of the photosensitive resin composition must be inhibited from yellowing, have excellent transparency, and be excellent in resistance to heat discoloration in the usage environment. can be done. In other words, it can be used as an index of the required characteristic.
Furthermore, the cured product of the photosensitive resin composition is required to have excellent durability such as solvent resistance in its application, and the required properties can be satisfied by satisfying the property (b). In other words, it can be used as an index of the required characteristic.
That is, since the cured product satisfies both the characteristics (a) and (b), the cured product can be suitably used for a color filter, a protective film such as a black matrix, etc. Imaging devices and the like will be excellent in product reliability.

Furthermore, it is preferable that a cured film having a film thickness of 3 μm obtained by heating the photosensitive resin composition of the present embodiment at 230° C. for 60 minutes satisfies the following property (c).
(c) The cured film has a 1% weight loss temperature (Td1) of 270°C or higher and a 5% weight loss temperature (Td5) of 330°C or higher.
Since the photosensitive resin composition of the present embodiment satisfies the characteristic (c), it is possible to provide a cured product having excellent heat resistance.

The cured product of the photosensitive resin composition is required to have excellent heat resistance in its application, and the required properties can be satisfied by satisfying the property (c). In other words, it can be used as an index of the required characteristic.
That is, when the cured product satisfies the characteristic (c), the cured product can be more preferably used as a protective film such as a color filter or a black matrix. Reliability is further improved.

In order to obtain a cured product that satisfies both properties (a) and (b) as well as property (c), a photosensitive resin composition containing a polymer containing structural units (1) to (5) and a polymerization initiator It can be achieved by using substances and preferably by setting the composition ratio of these components within a predetermined range.
Each component will be described below.

[polymer]
The polymer of this embodiment contains structural units (1) to (5) represented by the following general formulas (1) to (5).

In the present embodiment, from the viewpoint of the effect of the present invention, when the total of the structural units (1) to (5) is 100 mol%, the structural unit (1) is 0 to 10 mol%, the structural unit (4 ) is 0 to 10 mol%, and the total of structural units (2), (3) and (5) is preferably 80 to 100 mol%,
Structural unit (1) is 0 to 5 mol%, structural unit (4) is 0 to 5 mol%, and the total of structural units (2), (3) and (5) is 90 to 100 mol%. is more preferred.

Structural units (2), (3) and (5) are 20 to 40 mol% of structural unit (2) and 25 to 45 mol% of structural unit (3) when the total of these is 100 mol%. and the total amount of the structural units (5) is preferably 25 to 45 mol%,
It is preferable that the structural unit (2) is 25 to 35 mol %, the structural unit (3) is 30 to 40 mol %, and the total of the structural unit (5) is 30 to 40 mol %.

The content (ratio) of each structural unit contained in the polymer includes the charged amount (molar amount) of raw materials used when synthesizing the polymer, the amount of raw materials remaining after synthesis, various spectra (e.g., IR spectrum, It can be estimated/calculated from the presence of peaks in ¹ H-NMR spectrum, ¹³ C-NMR spectrum), peak area, and the like.
Each structural unit will be described below.

In structural unit (2) represented by general formula (2), Z is a group containing one or more (meth)acryloyl groups.
Z is not particularly limited as long as it is a group containing one or more (meth)acryloyl groups, more preferably a group containing 1 to 4 (meth)acryloyl groups, and 1 to 3 (meth)acryloyl groups It is more preferably a group containing one. By optimizing the number of (meth)acryloyl groups contained in Z, it is possible to obtain a cured product having excellent curability and heat resistance, as well as excellent durability such as transparency and solvent resistance.

From the viewpoint of these properties, Z is preferably a group containing one (meth)acryloyl group, more preferably a group represented by the following general formula (2-1).

In general formula (2-1), R is a hydrogen atom, a methyl group or an ethyl group.

In general formula (2), Q is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
Examples of alkyl groups 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. Examples of substituents of the substituted alkyl group having 1 to 6 carbon atoms include halogen atom, hydroxyl group, carboxyl group, amino group, cyano group, mercapto group and the like.

In general formula (2), X is an oxygen atom or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms.
The alkylene group includes a methylene group, an ethylene group, a propylene group and a butylene group. Examples of the substituted arylene group having 1 to 4 carbon atoms include a halogen atom, hydroxyl group, carboxyl group, amino group, cyano group and mercapto group.

In general formula (2), any carbon atom of the alkyl group of Q and the alkylene group of X may combine to form a ring. Examples of ring structures include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, decalin ring, benzene ring, and naphthalene ring.

In structural unit (3) represented by general formula (3), ^RA is a group containing one or more (meth)acryloyl groups.
R ^A is not particularly limited as long as it is a group containing one or more (meth)acryloyl groups, preferably a group containing 1 to 6 (meth)acryloyl groups, and 1 to 5 (meth)acryloyl groups A group containing 2 to 5 (meth)acryloyl groups is more preferable. By optimizing the number of (meth)acryloyl groups contained in ^RA , it is possible to obtain a cured product having excellent heat resistance and thus suppressing yellowing and having excellent transparency.

Examples of the structural unit (3) represented by the general formula (3) include structural units represented by the following general formula (3-1) and structural units represented by the following general formula (3-2). can be done.

In general formula (3-1), R 1 ^S is a group containing only one (meth)acryloyl group. In particular, in the design of ordinary photosensitive resin compositions, when the curability is increased in order to increase the sensitivity, the curing proceeds too much and the developability tends to deteriorate. Since curing tends to be insufficient in some cases, the polymer preferably contains a structural unit represented by the general formula (3-1), thereby achieving both sensitivity and developability in a good balance. be able to.

R 1 ^S is, for example, a group represented by general formula (3-1a) below.

In general formula (3-1a), 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 1-30, more preferably 1-20, even more preferably 1-10.
In general formula (3-1a), 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 1-30, more preferably 1-20, even more preferably 1-10.

As the divalent organic group for X ¹⁰ , for example, an alkylene group is preferable. A 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.

More preferably, the divalent organic group for X ¹⁰ is a linear alkylene group having 3 to 6 carbon atoms in total. By appropriately selecting the number of carbon atoms in X ¹⁰ (chain length of X ¹⁰ ), the structural unit represented by general formula (3-1) is more likely to participate in the cross-linking reaction, and the sensitivity can be increased. Furthermore, a cured product having excellent durability such as solvent resistance can be obtained.

The divalent organic group (eg, alkylene group) of X ¹⁰ may be substituted with any substituent. Examples of substituents include alkyl groups, aryl groups, alkoxy groups, and aryloxy groups.

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

In general formula (3-2), R ^D is not particularly limited as long as it is a group containing 2 or more (meth)acryloyl groups, but is more preferably a group containing 2 to 6 (meth)acryloyl groups. , a group containing 3 to 5 (meth)acryloyl groups. Curability can be further enhanced by optimizing the number of (meth)acryloyl groups contained in ^RD . Moreover, it becomes easy to make curability and developability compatible more highly. Furthermore, since the heat resistance can be increased more easily, a cured product having excellent transparency and durability such as solvent resistance can be obtained.

From the viewpoint of further improving curability, R ^D may contain two or more acryloyl groups (groups represented by -C(=O)-CH= _CH2 ) in terms of steric hindrance. preferable.

R ^D is preferably a group represented by the following general formula (3-2a), (3-2b) or (3-2c). With such a group, there is a tendency to easily obtain the various effects described above.

In general formula (3-2a),
k is 2 or 3,
R is a hydrogen atom or a methyl group, multiple R 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- (where Z is -O- or -OCO- and X is an alkylene group having 1 to 6 carbon atoms ), and multiple 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, Z' is -O- or -COO-),
X ² is a k+1 valent organic group having 1 to 12 carbon atoms.
R is preferably a hydrogen atom from the viewpoint of further improvement of sensitivity (ease of polymerization).
Although k may be 2 or 3, it is preferably 3 from the standpoints of availability of raw materials and further improvement of 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 group).

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), X has 1 to 6 carbon atoms Alkylene groups can be straight or branched.

The alkylene group having 1 to 6 carbon atoms of X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and 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, specific aspects thereof are the same as those of X ¹ .
When X ¹ ' is a group represented by -X'-Z'-, specific aspects of X' are the same as X above.

Examples of the k+1-valent organic group having 1 to 12 carbon atoms for X ² include any group obtained by removing k+1 hydrogen atoms from any organic compound. The “any organic compound” used herein is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, 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 linear hydrocarbon having 1 to 3 carbon atoms. In addition, the hydrocarbon here may contain an oxygen atom (for example, an ether bond, a hydroxy group, etc.). Also, the hydrocarbon is preferably a saturated hydrocarbon.

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

In general formula (3-2b),
k, R, X ¹ and X ² are respectively synonymous with R, k, X ¹ and X ² in the above general formula (3-2a), and a plurality of R may be the same or different. a plurality of X ¹ may be the same or different,
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 embodiments and preferred embodiments of R, k, X ¹ and X ² are the same as those described for general formula (3-2a).

Examples of the divalent organic group having 1 to 6 carbon atoms of X ³ and X ⁶ include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. can be done. In addition, the hydrocarbon here may contain an oxygen atom (for example, an ether bond, a hydroxy group, etc.). Also, the hydrocarbon is preferably a saturated hydrocarbon.

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

In general formula (3-2c), n is an integer of 2 to 5, preferably 2 or 3.

The proportion of the structural unit represented by general formula (3-2) in all structural units contained in the polymer of the present embodiment is preferably 1 to 30 mol%, more preferably 2 to 20 mol%.

The polymer of the present embodiment is a structural unit represented by the following general formula (6) consisting of a structural unit (2) represented by the general formula (2) and a structural unit (3) represented by the general formula (3). can include

In general formula (6), Z, Q and X have the same meanings as in general formula (2), and ^RA has the same meaning as in general formula (3).
The proportion of the structural unit represented by general formula (6) in the total structural units contained in the polymer of the present embodiment is preferably 30 to 50 mol%, more preferably 35 to 45 mol%.

The polymer of the present embodiment may contain a structural unit represented by the following general formula (7) consisting of a structural unit represented by general formula (2) and a structural unit represented by general formula (3-2). can.

In general formula (7), Q, X and Z have the same meanings as in general formula (2), and ^RD has the same meaning as in general formula (3-2).
The ratio of the structural unit represented by general formula (7) in all the structural units contained in the polymer of the present embodiment is preferably 0.25 to 17 mol%, more preferably 0.5 to 12 mol%. be.

The polymer of the present embodiment has a structural unit represented by the following general formula (8) as a structural unit composed of a structural unit represented by the general formula (2) and a structural unit represented by the general formula (3-1). can include

In general formula (8), Z, Q and X have the same meanings as in general formula (2), and R 2 ^S has the same meaning as in general formula (3-1).

When the polymer contains a structural unit represented by general formula (8), the proportion of the structural unit represented by general formula (8) in all structural units contained in the polymer is preferably 10 to 50 mol%, More preferably 20 to 45 mol %.

In structural unit (5) represented by general formula (5), 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.

Structural unit (5) represented by general formula (5) is chemically robust. Therefore, a polymer containing this as a structural unit undergoes little weight loss and is stable when subjected to heat treatment. Therefore, the photosensitive resin composition containing the polymer can be suitably used for producing films and filters for use in liquid crystal display devices and solid-state imaging devices that require 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 having 1 to 30 carbon atoms, more specifically alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, alkoxy group, heterocyclic group, carboxyl group and the like.

Examples of alkyl groups 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, heptyl group, octyl group, nonyl group, decyl group and the like.
Alkenyl groups include, for example, allyl groups, pentenyl groups, and vinyl groups.
Examples of alkynyl groups include ethynyl groups.
The alkylidene group includes, for example, a methylidene group and an ethylidene group.

Aryl groups include, for example, tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups.
The aralkyl group includes, for example, a benzyl group and a phenethyl group.
Examples of the alkaryl group include tolyl group and xylyl group.
Cycloalkyl groups include, for example, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, and neopentyloxy groups. , n-hexyloxy group and the like.
Heterocyclic groups include, for example, an epoxy group and an oxetanyl group.

R ¹ , R ² , R ³ and R ⁴ in the structural unit represented by general formula (5) are preferably hydrogen or alkyl groups, more preferably hydrogen.

The hydrogen atoms in the organic groups having 1 to 30 carbon atoms of R ¹ , R ² , R ³ and R ⁴ may be substituted with arbitrary atomic groups. For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, a fluorinated alkyl group or the like may be selected as the organic group having 1 to 30 carbon atoms for R ¹ , R ² , R ³ and R ⁴ .
In the structural unit represented by formula (5), a1 is preferably 0 or 1, more preferably 0.

The polymer of this embodiment can further contain a structural unit represented by the following general formula (9) and/or a structural unit represented by the following general formula (10).

In formula (9), ^RD has the same definition as in formula (3-2).
When the polymer contains a structural unit represented by general formula (9), the proportion of the structural unit represented by general formula (9) in all structural units contained in the polymer is preferably 0.5 to 25 mol. %, more preferably 1 to 18 mol %.

In general formula (10), R 2 ^S has the same meaning as in general formula (3-1).
When the polymer contains a structural unit represented by general formula (10), the proportion of the structural unit represented by general formula (10) in all structural units contained in the polymer is preferably 3 to 35 mol%, More preferably, it is 5 to 25 mol %.

The polymer of this embodiment may further contain other divalent structural units 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 (e.g., pinene, limonene, etc.), linear alkenes (e.g., pentene, etc.), cyclic alkenes (cyclohexene etc.), cyclododecatriene, tricycloundecaene, dialkyl fumarate (e.g., dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth)acrylic acid compounds (e.g., methyl methacrylate, methyl acrylate ), vinyl acetate, vinyl ether (eg, 2-hydroxyethyl vinyl ether, etc.) and the like.

Examples of substituents that these monomers may have include alkyl groups and aryl groups. More specifically, substituted indene includes methylindene and the like. Substituted maleimides include cyclohexylmaleimide, phenylmaleimide and the like. Examples of substituted styrene include methylstyrene and vinyltoluene.

Among them, Chain is preferably a structural unit represented by general formula (a) (a divalent structural unit derived from substituted or unsubstituted indene), a structural unit represented by general formula (b) (substituted or divalent structural unit derived from unsubstituted maleimide), structural unit represented by general formula (c) (divalent structural unit derived from substituted or unsubstituted styrene), or general formula (9) (a divalent structural unit derived from substituted or unsubstituted norbornadiene) represented by

In general formula (a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group. In general formula (b) ^, R3 represents a hydrogen atom, an alkyl group or an aryl group. In general formula (c), R ⁴ to R ⁶ each independently represent a hydrogen atom, an alkyl group or an aryl group. In general formula (9), R ⁷ to R ¹⁰ each independently represent a hydrogen atom, a hydroxyl group or an organic group having 1 to 30 carbon atoms.

The polymer of the present embodiment may be bonded via a thioether group derived from at least one thiol group of a thiol group-containing compound having a functionality of two or more.
Specifically, it has a structure in which at least one polymer chain represented by the following Chain is bonded to a monovalent to hexavalent organic group having 1 to 30 carbon atoms derived from a difunctional or more thiol group-containing compound. . Specifically, the polymer of this embodiment can be represented by the following general formula (P).

In general formula (P), Chain is the aforementioned polymer chain containing the structural units of general formulas (1) to (5).

In the general formula (P), Y is a mono- to hexavalent organic group (i) having 1 or more and 30 or less carbon atoms derived from a compound containing a thiol group having a functionality of 2 or more.

In this embodiment, the number of functional groups is the number of thiol groups. That is, the thiol group-containing compound contains two or more thiol groups, and the organic group (i) binds to Chain via 1 to 6 thioether groups derived from the thiol groups. The organic group (i) may have a thiol group that does not participate in bonding with Chain, and the polymer can be obtained as a mixture of resins having n (number of bonds) of 1 to 6. .

The organic group (i) having 1 to 30 carbon atoms is bifunctional or more, preferably 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 valence, preferably 2 to 6 valence, more preferably 3 to 6 valence, from the viewpoint of the effects 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 monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms include alkyl groups, alkenyl groups, Examples include alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups and heterocyclic groups.

Examples of alkyl groups 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. , octyl, nonyl, and decyl groups. Alkenyl groups include, for example, allyl groups, pentenyl groups, and vinyl groups.

Alkynyl groups include ethynyl groups.
The alkylidene group includes, for example, a methylidene group and an ethylidene group. Aryl groups include, for example, tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups.
Aralkyl groups include, for example, benzyl groups and phenethyl groups.
The alkaryl group includes, for example, a tolyl group and a xylyl group.

Cycloalkyl groups include, for example, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy, isobutoxy, t-butoxy, n-pentyloxy, and neopentyloxy groups. , and n-hexyloxy groups.
Heterocyclic groups include, for example, epoxy groups and oxetanyl groups.

Examples of the bifunctional or higher thiol group-containing compound include compounds represented by the following chemical formulas (s-1) to (s-20).

The bifunctional or higher thiol group-containing compounds may be used singly or in combination of two or more.
The monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms is a thioether group (-S-* (* is a bond)) derived from the thiol group of these thiol group-containing compounds. It has a thioether group and binds to the structural unit contained in the chain. The organic group (i) may have a thiol group that does not participate in bonding with Chain.

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

In general formula (P'), Chain and Y are synonymous with general formula (P). p is an integer of 1 or more, q is an integer of 0 or more, and p+q is 1-6.
Q is

Q, which is a structure other than Chain, is not particularly limited as long as it can be bonded to Y, and various components used in the synthesis reaction can be mentioned. Units (structural units represented by the general formula (7) and/or structural units represented by the general formula (8)), structural units represented by the general formula (9), general formula (10) A structural unit represented by the general formula (5), a structural unit represented by the general formula (4), and a divalent derived from a copolymerizable compound having a double bond Examples include at least one selected from structural units and groups derived from the above bifunctional or higher thiol group-containing compounds.

When the compound represented by the chemical formula (s-2) is used as the difunctional or higher thiol group-containing compound, the polymer of the present embodiment has a structure represented by the following general formula (I), for example. can have

In general formula (I), Chain has the same definition as in general formula (P1), and the structures of the four Chains may be the same or different.

In the general formula (I), an example in which four Chains are bonded via thioether groups derived from four mercapto groups of the compound represented by the chemical formula (s-2) is shown. It may be a structure in which 1 to 3 are bonded. The Q may be bonded to the remaining thioether groups. In this embodiment, the polymer can be obtained as a mixture containing at least one compound having 1 to 4 chains.

The weight average molecular weight Mw of the polymer is, for example, 1,000 to 15,000, preferably 1,500 to 12,000, more preferably 2,000 to 10,000, still more preferably 3,000 to 8. , 000. By appropriately adjusting the weight average molecular weight, it is possible to adjust sensitivity and solubility in an alkaline developer.

Further, the degree of dispersion of the polymer (weight average molecular weight Mw/number average molecular weight Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, still more preferably 1.0 to 3.0. is. By appropriately adjusting the degree of dispersion, the physical properties of the polymer can be made uniform, which is preferable. These values can be obtained by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

The glass transition temperature of the polymer is preferably 150-250°C, more preferably 170-230°C. The polymer has a relatively high glass transition temperature mainly due to the inclusion of structural units represented by general formula (5). This is preferable in that the pattern formed on the substrate can exist stably in manufacturing liquid crystal display devices and solid-state imaging devices. The glass transition temperature can be determined by, for example, differential thermal analysis (DTA).

From the viewpoint of the effect of the present invention, the polymer of the present embodiment is preferably 10% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 35% by mass or less in 100% by mass of the photosensitive resin composition. can be included in

<Method for producing polymer>
The method for producing the polymer of the present embodiment will be described using the method for producing the polymer represented by the general formula (P) as an example.
A polymer can be manufactured (synthesized) by any method. For example, the polymer
Step (I): a structural unit represented by general formula (5), a structural unit represented by general formula (4), and the organic group (i) having 1 to 6 valent carbon atoms and having 1 to 30 carbon atoms; preparing a raw material polymer comprising
and/ Or a compound having a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as a "monofunctional (meth)acrylic monomer") is reacted in the presence of a basic catalyst to obtain a compound represented by the general formula (5). the structural unit, the monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, the structural unit represented by the general formula (9) and / or the structural unit represented by the general formula (10), A step of optionally preparing a polymer precursor containing a structural unit represented by the general formula (4), and a step (III): The polymer precursor obtained in step (II) is treated with an epoxy group-containing (Meth) by reacting with an acrylic compound, the structural unit represented by the general formula (5), the organic group (i) having 1 to 6 valent carbon atoms and 30 or less, represented by the general formula (9) Structural units and / or structural units represented by general formula (10), structural units represented by general formula (6) (structural units represented by general formula (7) and / or structural units represented by general formula (8) structural unit), optionally a step of preparing a polymer containing a structural unit represented by general formula (4),
can be manufactured by

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 starting polymer, and the resulting reaction mixture is added with It is preferable to react a monofunctional (meth)acrylic monomer.

(Step (I))
In step (I), a structural unit represented by general formula (5), a structural unit represented by general formula (4), and the monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms The step of preparing a raw material polymer containing a monomer represented by the general formula (5′) and a monomer composition containing maleic anhydride in the presence of the above-mentioned difunctional or higher thiol group-containing compound, polymerizing It can be carried out by (addition polymerization). The definitions of R ¹ , R ² , R ³ and R ⁴ and a1 in general formula (5′) are the same as those in general formula (5). The same applies to preferred embodiments.

Monomers represented by the general formula (5′) include, 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-carboxylate methyl, 5-norbornene-2,3-dicarboxylic anhydride and the like. At the time of polymerization, the monomer represented by general formula (5') 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 known compounds can be used, and can be polymerized with the monomer represented by the general formula (5′) and maleic anhydride. . Other monomers include, for example, substituted or unsubstituted indene, maleimide, styrene, acenaphthylene, norbornadiene, dihydrofuran, terpene compounds (e.g., pinene, limonene, etc.), linear alkenes (e.g., pentene, etc.), cyclic alkenes. (cyclohexene, etc.), cyclododecatriene, tricycloundecaene, dialkyl fumarate (e.g., dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth)acrylic acid compounds (e.g., methyl methacrylate, acrylic acid methyl), vinyl acetate, vinyl ether (eg, 2-hydroxyethyl vinyl ether, etc.), and the like. In step (I), a monomer represented by the general formula (5′), maleic anhydride, and optionally other monomers are combined in the presence of the difunctional or higher thiol group-containing compound, It can be polymerized (addition polymerized).

Examples of the bifunctional or higher thiol group-containing compound include, but are not limited to, the compounds represented by the chemical formulas (s-1) to (s-20). The bifunctional or higher thiol group-containing compounds may be used singly or in combination of two or more.

Although the polymerization method is not limited, radical polymerization using a radical polymerization initiator is preferred. Examples of polymerization initiators that can be used include azo compounds and organic peroxides.
Specific examples of azo compounds include azobisisobutyronitrile (AIBN), dimethyl 2,2′-azobis(2-methylpropionate), 1,1′-azobis(cyclohexanecarbonitrile) (ABCN), and the like. can be mentioned.
Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP).
As for the polymerization initiator, only one type may be used, or two or more types may be used in combination.

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

In the synthesis of the raw material polymer, the monomer represented by the general formula (5′), maleic anhydride and a polymerization initiator are dissolved in a solvent and charged into a reaction vessel, and then heated to form a bifunctional or higher thiol group-containing It is carried out by allowing the addition polymerization to proceed while dropping the compound. The heating temperature is, for example, 50 to 80° C., and the heating time is, for example, 5 to 20 hours.
The molar ratio of the monomer represented by the general formula (5') to maleic anhydride when charged into the reactor is preferably 0.5:1 to 1:0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 1:1.
A "raw material polymer" can be obtained by such a process.
The raw material polymer may be any of random copolymers, alternating copolymers, block copolymers, periodic copolymers, and the like. Typically they are random or alternating copolymers. Maleic anhydride is generally known as a monomer having strong alternating copolymerizability.

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

(Step (II))
By reacting the raw material polymer obtained in step (I) with a polyfunctional (meth)acrylic monomer and/or a monofunctional (meth)acrylic monomer in the presence of a basic catalyst, the general A part of the structural unit represented by formula (4) is ring-opened to form a structural unit represented by general formula (9) and/or a structural unit represented by general formula (10). Thereby, the structural unit represented by the general formula (5), the organic group (i) having 1 to 6 valent carbon atoms and 30 or less, and the structural unit represented by the general formula (9) and / or general A polymer precursor containing a structural unit represented by formula (10) and optionally containing a structural unit represented by general formula (4) is obtained.

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

When obtaining a polymer containing both structural units represented by general formula (5) and structural units represented by general formula (9) and general formula (10), then the above A polyfunctional (meth)acrylic monomer is added to the solution. Additionally, a basic catalyst is added. Then, the solution is appropriately mixed to form a uniform solution, and at least the structural unit of general formula (5) and the structural unit of general formula (9) are combined with the organic group (i) having 1 to 30 carbon atoms and 1 to A polymer containing a structure bonded via six thioether groups is obtained (step (II-i)).

Polyfunctional (meth) acrylic monomers that can be used here include, for example, compounds represented by general formula (3-2a′), compounds represented by general formula (3-2b′), and general formula (3 -2c'). ^The definitions and specific embodiments of k, R, X1, X1' and X2 in general formula (3-2a') are the same as in general formula (3-2a) above. The definitions and specific embodiments of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in general formula (3-2b′) are those in general formula (3-2b) above. is similar to n in general formula (3-2c′) is the same as in general formula (3-2c) above.

Preferred usable polyfunctional (meth)acrylic compounds having a hydroxy group are shown below. In addition, it is also possible to use the compounds shown below in which part or all of the acryloyl groups are (meth)acryloyl groups (or vice versa).

Then, the polymer obtained in step (II-i) is reacted with a monofunctional (meth)acrylic monomer in the presence of a basic catalyst to obtain at least the structural unit of general formula (5), general formula (9 ) and a structural unit of the general formula (10) are bonded to the organic group (i) having 1 to 30 carbon atoms via 1 to 6 thioether groups. (Step (II-ii)).

As the basic catalyst, amine compounds, nitrogen-containing heterocyclic compounds, and the like, which are known in the field of organic synthesis, can be appropriately used. For example, an amine compound such as triethylamine, pyridine, dimethylaminopyridine, or a nitrogen-containing heterocyclic compound can be used as a catalyst. 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 starting polymer. It should be noted that if the basic catalyst is used excessively, the amount of acid required for neutralization increases, which may complicate purification.

The above solution is preferably heated at 60 to 80° C. for about 3 to 9 hours to open the structural unit of the general formula (4) contained in the raw material polymer/form the structural unit of the general formula (6). is done.

Incidentally, for example, by adding a monofunctional (meth)acrylic compound having a hydroxy group to the reaction system during the above heating, the structural unit represented by the above general formula (8) is added to the polymer. can be generated.

From the viewpoint of reaction steric hindrance, a monofunctional (meth)acrylic compound having a hydroxy group tends to react more easily with a raw material polymer than a polyfunctional (meth)acrylic compound having a hydroxy group. Therefore, when the structural unit represented by the above general formula (8) is generated in the polymer, a monofunctional (meth)acrylic compound having a hydroxy group is not charged into the reaction system from the beginning, and It is preferable to append to
Monofunctional (meth)acrylic compounds having a hydroxy group include, for example, compounds represented by the following general formula (3-1a').
In general formula (3-1a'), the definitions of X ¹⁰ and R are the same as in general formula (3-1a).

Specific examples of the compound represented by the general formula (3-1a′) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-(meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, etc. can be mentioned.

The structural unit represented by the general formula (5), the organic group (i) having 1 to 6 valent carbon atoms and 30 or less, and the structural unit represented by the general formula (6) and the general formula (7) When obtaining a polymer containing either one of the represented structural units, only one of the steps (II-i) and (II-ii) may be carried out after the step (I).

(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 convert the carboxyl group of the polymer precursor and the epoxy group of the epoxy group-containing (meth)acrylic compound into A structural unit represented by general formula (6) (a structural unit represented by general formula (7) and/or a structural unit represented by general formula (8)) is formed. Thereby, the structural unit represented by the general formula (5), the organic group (i) having 1 to 6 carbon atoms and 30 or less monovalent to hexavalent, the structural unit represented by the general formula (9) and / or the general formula The structural unit represented by (10), the structural unit represented by the general formula (6) (the structural unit represented by the general formula (7) and/or the structural unit represented by the general formula (8)), the case A polymer containing a structural unit represented by general formula (4) is prepared by:

Step (III) is preferably carried out by adding an epoxy group-containing (meth)acrylic compound to the reaction system containing the polymer precursor obtained in step (II-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, the 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 neutralized. It is preferable to add the epoxy group-containing (meth)acrylic compound in situ to the reaction mixture containing the polymer precursor obtained in step (II-ii) without the addition of the epoxy group-containing (meth)acryl compound.

Specifically, the reaction solution obtained by adding the epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor is preferably heated at 60 to 80° C. for about 1 to 9 hours, A structural unit represented by general formula (6) (a structural unit represented by general formula (7) and/or A structural unit represented by the general formula (8)) is formed to produce a polymer.

Examples of epoxy group-containing (meth)acrylic compounds include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and acrylic acid. Glycidyl and the like can be mentioned, and one or more selected from these can be used.

The amount of the epoxy group-containing (meth)acrylic compound to be added is desirably 0.1 to 3.0 mol per 1 mol of the carboxyl group of the polymer precursor.

After step (III), the following steps are preferably carried out as appropriate in order to remove unnecessary components other than the desired polymer.

First, the above reaction solution diluted with an organic solvent and added with an acid (eg, formic acid, citric acid, etc.) is vigorously stirred in a separatory funnel for at least 3 minutes. This is allowed to stand still for 30 minutes or more, separated into an organic phase and an aqueous phase, and the aqueous phase is removed. An organic solution of the polymer is thus obtained.

An excess amount of toluene is added to the resulting organic solution of the polymer to reprecipitate the polymer. In addition, the polymer powder obtained by reprecipitation is further washed with toluene several times (for example, twice).
Further, the operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (for example, three times) in order to remove the acid and basic catalyst.
By drying the polymer powder after washing with ion-exchanged water, for example, at 30 to 60° C. for 16 hours or more, a highly pure polymer of the present embodiment can be obtained.

<Method for producing polymer>
A method for producing the polymer of the present embodiment will be described.
A polymer can be manufactured (synthesized) by any method. Polymers are, for example,
Step (I): a structural unit represented by general formula (5), a structural unit represented by general formula (4), and the organic group (i) having 1 to 6 valent carbon atoms and having 1 to 30 carbon atoms; preparing a raw material polymer comprising
and/ Or a compound having a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as a "monofunctional (meth)acrylic monomer") is reacted in the presence of a basic catalyst to obtain a compound represented by the general formula (5). the structural unit, the monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms, the structural unit represented by the general formula (9) and / or the structural unit represented by the general formula (10), A step of optionally preparing a polymer precursor containing a structural unit represented by the general formula (4), and a step (III): The polymer precursor obtained in step (II) is treated with an epoxy group-containing (Meth) by reacting with an acrylic compound, the structural unit represented by the general formula (5), the organic group (i) having 1 to 6 valent carbon atoms and 30 or less, represented by the general formula (9) Structural units and / or structural units represented by general formula (10), structural units represented by general formula (6) (structural units represented by general formula (7) and / or structural units represented by general formula (8) structural unit), optionally a step of preparing a polymer containing a structural unit represented by general formula (4),
can be manufactured by

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 starting polymer, and the resulting reaction mixture is added with It is preferable to react a monofunctional (meth)acrylic monomer.

(Step (I))
In step (I), a structural unit represented by general formula (5), a structural unit represented by general formula (4), and the monovalent to hexavalent organic group (i) having 1 to 30 carbon atoms The step of preparing a raw material polymer containing a monomer represented by the general formula (5′) and a monomer composition containing maleic anhydride in the presence of the above-mentioned difunctional or higher thiol group-containing compound, polymerizing It can be carried out by (addition polymerization). The definitions of R ¹ , R ² , R ³ and R ⁴ and a1 in general formula (5′) are the same as those in general formula (5). The same applies to preferred embodiments.

Monomers represented by the general formula (5′) include, 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-carboxylate methyl, 5-norbornene-2,3-dicarboxylic anhydride and the like. At the time of polymerization, the monomer represented by general formula (5') 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 known compounds can be used, and can be polymerized with the monomer represented by the general formula (5′) and maleic anhydride. . Other monomers include, for example, substituted or unsubstituted indene, maleimide, styrene, acenaphthylene, norbornadiene, dihydrofuran, terpene compounds (e.g., pinene, limonene, etc.), linear alkenes (e.g., pentene, etc.), cyclic alkenes. (cyclohexene, etc.), cyclododecatriene, tricycloundecaene, dialkyl fumarate (e.g., dimethyl fumarate, ethyl fumarate, dibutyl fumarate, etc.), coumarin, (meth)acrylic acid compounds (e.g., methyl methacrylate, acrylic acid methyl), vinyl acetate, vinyl ether (eg, 2-hydroxyethyl vinyl ether, etc.), and the like. In step (I), a monomer represented by the general formula (5′), maleic anhydride, and optionally other monomers are combined in the presence of the difunctional or higher thiol group-containing compound, It can be polymerized (addition polymerized).

Examples of the bifunctional or higher thiol group-containing compound include, but are not limited to, the compounds represented by the chemical formulas (s-1) to (s-20). The bifunctional or higher thiol group-containing compounds may be used singly or in combination of two or more.

Although the polymerization method is not limited, radical polymerization using a radical polymerization initiator is preferred. Examples of polymerization initiators that can be used include azo compounds and organic peroxides.
Specific examples of azo compounds include azobisisobutyronitrile (AIBN), dimethyl 2,2′-azobis(2-methylpropionate), 1,1′-azobis(cyclohexanecarbonitrile) (ABCN), and the like. can be mentioned.
Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP).
As for the polymerization initiator, only one type may be used, or two or more types may be used in combination.

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

In the synthesis of the raw material polymer, the monomer represented by the general formula (5′), maleic anhydride and a polymerization initiator are dissolved in a solvent and charged into a reaction vessel, and then heated to form a bifunctional or higher thiol group-containing It is carried out by allowing the addition polymerization to proceed while dropping the compound. The heating temperature is, for example, 50 to 80° C., and the heating time is, for example, 5 to 20 hours.
The molar ratio of the monomer represented by the general formula (5') to maleic anhydride when charged into the reactor is preferably 0.5:1 to 1:0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 1:1.
A "raw material polymer" can be obtained by such a process.
The raw material polymer may be any of random copolymers, alternating copolymers, block copolymers, periodic copolymers, and the like. Typically they are random or alternating copolymers. Maleic anhydride is generally known as a monomer having strong alternating copolymerizability.

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

(Step (II))
By reacting the raw material polymer obtained in step (I) with a polyfunctional (meth)acrylic monomer and/or a monofunctional (meth)acrylic monomer in the presence of a basic catalyst, the general A part of the structural unit represented by formula (4) is ring-opened to form a structural unit represented by general formula (9) and/or a structural unit represented by general formula (10). Thereby, the structural unit represented by the general formula (5), the organic group (i) having 1 to 6 valent carbon atoms and 30 or less, and the structural unit represented by the general formula (9) and / or general A polymer precursor containing a structural unit represented by formula (10) and optionally containing a structural unit represented by general formula (4) is obtained.

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

When obtaining a polymer containing both structural units represented by general formula (5) and structural units represented by general formula (9) and general formula (10), then the above A polyfunctional (meth)acrylic monomer is added to the solution. Additionally, a basic catalyst is added. Then, the solution is appropriately mixed to form a uniform solution, and at least the structural unit of general formula (5) and the structural unit of general formula (9) are combined with the organic group (i) having 1 to 30 carbon atoms and 1 to A polymer containing a structure bonded via six thioether groups is obtained (step (II-i)).

Polyfunctional (meth) acrylic monomers that can be used here include, for example, compounds represented by general formula (3-2a′), compounds represented by general formula (3-2b′), and general formula (3 -2c'). ^The definitions and specific embodiments of k, R, X1, X1' and X2 in general formula (3-2a') are the same as in general formula (3-2a) above. The definitions and specific embodiments of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in general formula (3-2b′) are those in general formula (3-2b) above. is similar to n in general formula (3-2b') is the same as in general formula (3-2c) above.

Preferred usable polyfunctional (meth)acrylic compounds having a hydroxy group are shown below. In addition, it is also possible to use the compounds shown below in which part or all of the acryloyl groups are (meth)acryloyl groups (or vice versa).

Then, the polymer obtained in step (II-i) is reacted with a monofunctional (meth)acrylic monomer in the presence of a basic catalyst to obtain at least the structural unit of general formula (5), general formula (9 ) and a structural unit of the general formula (10) are bonded to the organic group (i) having 1 to 30 carbon atoms via 1 to 6 thioether groups. (Step (II-ii)).

As the basic catalyst, amine compounds, nitrogen-containing heterocyclic compounds, and the like, which are known in the field of organic synthesis, can be appropriately used. For example, an amine compound such as triethylamine, pyridine, dimethylaminopyridine, or a nitrogen-containing heterocyclic compound can be used as a catalyst. 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 starting polymer. It should be noted that if the basic catalyst is used excessively, the amount of acid required for neutralization increases, which may complicate purification.

The above solution is preferably heated at 60 to 80° C. for about 3 to 9 hours to open the structural unit of the general formula (4) contained in the raw material polymer/form the structural unit of the general formula (6). is done.

Incidentally, for example, by adding a monofunctional (meth)acrylic compound having a hydroxy group to the reaction system during the above heating, the structural unit represented by the above general formula (8) is added to the polymer. can be generated.

From the viewpoint of reaction steric hindrance, a monofunctional (meth)acrylic compound having a hydroxy group tends to react more easily with a raw material polymer than a polyfunctional (meth)acrylic compound having a hydroxy group. Therefore, when the structural unit represented by the above general formula (8) is generated in the polymer, a monofunctional (meth)acrylic compound having a hydroxy group is not charged into the reaction system from the beginning, and It is preferable to append to
Monofunctional (meth)acrylic compounds having a hydroxy group include, for example, compounds represented by the following general formula (3-1a').
In general formula (3-1a'), the definitions of X ¹⁰ and R are the same as in general formula (3-1a).

Specific examples of the compound represented by the general formula (3-1a′) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-(meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, etc. can be mentioned.

The structural unit represented by the general formula (5), the organic group (i) having 1 to 6 valent carbon atoms and 30 or less, and the structural unit represented by the general formula (6) and the general formula (7) When obtaining a polymer containing either one of the represented structural units, only one of the steps (II-i) and (II-ii) may be carried out after the step (I).

(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 convert the carboxyl group of the polymer precursor and the epoxy group of the epoxy group-containing (meth)acrylic compound into A structural unit represented by general formula (6) (a structural unit represented by general formula (7) and/or a structural unit represented by general formula (8)) is formed. Thereby, the structural unit represented by the general formula (5), the organic group (i) having 1 to 6 carbon atoms and 30 or less monovalent to hexavalent, the structural unit represented by the general formula (9) and / or the general formula The structural unit represented by (10), the structural unit represented by the general formula (6) (the structural unit represented by the general formula (7) and/or the structural unit represented by the general formula (8)), the case A polymer containing a structural unit represented by general formula (4) is prepared by:

Step (III) is preferably carried out by adding an epoxy group-containing (meth)acrylic compound to the reaction system containing the polymer precursor obtained in step (II-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, the 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 neutralized. It is preferable to add the epoxy group-containing (meth)acrylic compound in situ to the reaction mixture containing the polymer precursor obtained in step (II-ii) without the addition of the epoxy group-containing (meth)acryl compound.

Specifically, the reaction solution obtained by adding the epoxy group-containing (meth)acrylic compound to the reaction mixture containing the polymer precursor is preferably heated at 60 to 80° C. for about 1 to 9 hours, A structural unit represented by general formula (6) (a structural unit represented by general formula (7) and/or A structural unit represented by the general formula (8)) is formed to produce a polymer.

Examples of epoxy group-containing (meth)acrylic compounds include glycidyl methacrylate (GMA), 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and acrylic acid. Glycidyl and the like can be mentioned, and one or more selected from these can be used.

The amount of the epoxy group-containing (meth)acrylic compound to be added is desirably 0.1 to 3.0 mol per 1 mol of the carboxyl group of the polymer precursor.

After step (III), the following steps are preferably carried out as appropriate in order to remove unnecessary components other than the desired polymer.

First, the above reaction solution diluted with an organic solvent and added with an acid (eg, formic acid, citric acid, etc.) is vigorously stirred in a separatory funnel for at least 3 minutes. This is allowed to stand still for 30 minutes or more, separated into an organic phase and an aqueous phase, and the aqueous phase is removed. An organic solution of the polymer is thus obtained.

An excess amount of toluene is added to the resulting organic solution of the polymer to reprecipitate the polymer. In addition, the polymer powder obtained by reprecipitation is further washed with toluene several times (for example, twice).
Further, the operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (for example, three times) in order to remove the acid and basic catalyst.
By drying the polymer powder after washing with ion-exchanged water, for example, at 30 to 60° C. for 16 hours or more, a highly pure polymer of the present embodiment can be obtained.

[Polymerization initiator]
A photoradical polymerization initiator is mentioned as a polymerization initiator which is contained together with the polymer in the photosensitive resin composition of the present embodiment. As the radical photopolymerization initiator, known compounds can be used. 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-morpholinopropan-1-one, 2 -benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) ) phenyl]-1-butanone and other alkylphenone compounds; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone and other benzophenone compounds; benzoin compounds such as benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4- methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)- Halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; 2-trichloromethyl -5-(2′-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-benzofuryl)vinyl]-1,3,4-oxadiazole, 4 -oxadiazole, halomethylated oxadiazole compounds such as 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) -Biimidazole compounds such as 4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and other oxime ester compounds; bis(η5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium compounds such as titanocene compounds; p-dimethylaminobenzoic acid, p -benzoic acid ester compounds such as diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine; A photoradical polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.
The radical photopolymerization initiator is used in an amount of, for example, 1 to 20 parts by weight, preferably 3 to 10 parts by weight, per 100 parts by weight of the polymer.

Since the photosensitive resin composition of the present embodiment contains the above components, it has high sensitivity in photolithography processing and excellent alkali solubility. Therefore, the photosensitive resin composition has excellent developability and excellent processability in photolithography. In addition, since yellowing of the photosensitive resin composition is suppressed, an article obtained by curing the photosensitive resin composition has transparency.

[Polyfunctional (meth)acrylic compound]
The photosensitive resin composition of this embodiment can contain a polyfunctional (meth)acrylic compound.
A conventionally known compound can be used as the polyfunctional (meth)acrylate compound, which is a compound having two or more (meth)acryloyl groups, as long as the effects of the present invention can be exhibited.

Examples of polyfunctional (meth) acrylic compounds include compounds represented by the following general formula (3-2p), compounds represented by general formula (3-2q), and general formula (3-2r). Examples include, but are not limited to, compounds described in

The definitions and specific embodiments of k, R, X ¹ , X ¹ ' and X ² in general formula (3-2p) are the same as in general formula (3-2a) above. The definitions and specific embodiments of k, R, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ in general formula (3-2q) are the same as in general formula (3-2b) above. It is the same.

Y in general formulas (3-2p), (3-2q) and (3-2r) is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

Compounds in which Y is a hydrogen atom in general formulas (3-2p), general formulas (3-2q) and general formulas (3-2r) are unreacted monomers (that is, general formulas (3-2p), general formulas ( 3-2q) and a compound represented by general formula (3-2r)), which can be added separately.
n in the general formula (3-2r) is an integer of 2 or more, preferably an integer of 2-5, more preferably an integer of 2-3.

Specific examples of the polyfunctional (meth)acrylic compound represented by general formula (3-2p) include, but are not limited to, compounds having the following structures. In the compounds below, Y represents a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

Specific examples of the polyfunctional (meth)acrylic compound represented by general formula (3-2q) include, but are not limited to, the following compounds.

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

[Monofunctional (meth)acrylic compound]
The photosensitive resin composition of the present embodiment may contain a monofunctional (meth)acrylic compound that is a compound having one (meth)acryloyl group.

Monofunctional (meth)acrylic compounds include compounds represented by the following general formula (3-1a′). The monofunctional (meth)acrylic compound may be an unreacted monomer or may be added separately.
In general formula (3-1a'), the definitions of X ¹⁰ and R are the same as in general formula (3-1a).

Specific examples of the compound represented by the general formula (3-1a′) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-(meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, etc. can be 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 effects of the present invention. The peak area derived from the functional (meth)acrylic compound can be blended in such an amount that the peak area of the resin is preferably 10% or less, more preferably 5% or less, and still more preferably 2% or less.

[Coloring agent]
The photosensitive resin composition of this embodiment can contain a colorant. By containing a coloring agent, it can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state imaging device. Various pigments or dyes can be used as colorants.
An organic pigment or an inorganic pigment can be used as the pigment.

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

Inorganic pigments include white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellow, cadmium-based, chrome vermillion, nickel titanium, chrome titanium , yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine blue, navy blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments ( zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.

As the dye, for example, known dyes described in JP-A-2003-270428, JP-A-9-171108, JP-A-2008-50599, etc. can be used.
When the photosensitive resin composition contains a coloring agent, the photosensitive resin composition may contain only one coloring agent, or may contain two or more coloring agents.

Colorants (particularly pigments) having an appropriate average particle size can be used depending on the purpose and application. Particle size is preferred, and when concealing properties such as paint are required, a large average particle size of 0.5 μm or more is preferred.

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

When the photosensitive resin composition contains a colorant, the amount thereof may be appropriately set according to the purpose and application. It is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 50% by mass, based on the total components (components excluding the solvent).

(Surfactant)
The photosensitive resin composition of the present embodiment can contain a surfactant, and the surfactant is preferably a nonionic surfactant.

By including a nonionic surfactant, the coating properties of the photosensitive resin composition are improved when a resin film is obtained by applying the composition onto a substrate, and a coating film having a uniform thickness can be obtained. In addition, it is possible to prevent residues and patterns from rising when the coating film is developed.

A nonionic surfactant is, for example, a compound containing a fluorine group (eg, 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 fluorine-based surfactant or a silicone-based surfactant as the nonionic surfactant, and it is particularly preferable to use a fluorine-based surfactant. Examples of fluorosurfactants include Megafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477 and F manufactured by DIC Corporation. -554, F-556, and F-557, Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited, and the like, but are not limited thereto.
When a surfactant is used, the amount of the surfactant to be blended is preferably 0.01 to 10% by weight with respect to 100 parts by mass of the resin.

(solvent)
The photosensitive resin composition of this embodiment can typically contain a solvent. An organic solvent is preferably used as the solvent. Specifically, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, and the like can be used.

Examples of solvents 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, cyclohexanone, or mixtures thereof.
The amount of the solvent used is not particularly limited, but it is used in such an amount that the concentration of non-volatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

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

When the photosensitive resin composition contains a light-shielding agent, the amount thereof may be appropriately set according to the purpose and application. It is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 50% by mass, based on the total components (components excluding the solvent).

(crosslinking agent)
The photosensitive resin composition of this embodiment can contain a cross-linking agent.
The cross-linking agent is not particularly limited as long as it can cross-link the polymer (can chemically bond with the polymer) by the action of the active chemical species generated from the photopolymerization initiator.
The cross-linking agent may not only chemically bond with the polymer, but may react with each other to form a bond.

The cross-linking agent is, for example, preferably a polyfunctional compound having two or more polymerizable double bonds in one molecule, and a polyfunctional (meth) acrylic compound having two or more (meth)acryloyl groups in one molecule. is more preferred (but the cross-linking agent does not fall under the aforementioned polymers). It is preferable to use a cross-linking agent having the same type of cross-linking group as the cross-linking group (polymerizable double bond) of the polymer from the viewpoint of uniform curability and further improvement of sensitivity.
Although there is no particular upper limit to the number of functionalities (the number of polymerizable double bonds) per molecule of the cross-linking agent, it is, for example, 8 or less, preferably 6 or less.

Specific examples of cross-linking agents include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, (meth)acrylates, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth) Acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added ditrimethylol Propane 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 Acrylates, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate , ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) acrylate, polyfunctional (meth) acrylates;
Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditri Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide Polyfunctional vinyl ethers such as adduct dipentaerythritol hexavinyl ether;
2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4 (meth) acrylic acid -vinyloxybutyl, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, ( Vinyl ether group-containing (meth) such as p-vinyloxymethylphenylmethyl meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate 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 pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, Polyfunctional allyl ethers such as ethylene oxide-added pentaerythritol tetraallyl ether and ethylene oxide-added dipentaerythritol hexaallyl ether;
Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate;
Polyfunctional (meth)acryloyl such as tri(acryloyloxyethyl) isocyanurate, tri(methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri(acryloyloxyethyl) isocyanurate, alkylene oxide-added tri(methacryloyloxyethyl) isocyanurate group-containing isocyanurates;
Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate;
Reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate and xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate Polyfunctional urethane (meth) acrylates obtained in;
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, tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate ) acrylate and hexafunctional (meth)acrylate such as dipentaerythritol hexa(meth)acrylate are preferred.

When the photosensitive resin composition contains a cross-linking agent, the photosensitive resin composition may contain only one cross-linking agent, or two or more cross-linking agents. When the photosensitive resin composition contains a cross-linking agent, the amount thereof may be appropriately set according to the purpose and application. As an example, the amount of the cross-linking agent can be usually about 30 to 70 parts by weight, preferably about 40 to 60 parts by weight, per 100 parts by weight of the photosensitive resin.

(other ingredients)
Depending on various purposes and required properties, the photosensitive resin composition may contain fillers, binder resins other than the above polymers, acid generators, heat resistance improvers, development aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, oxidation Ingredients such as inhibitors, matting agents, antifoaming agents, leveling agents, antistatic agents, dispersing agents, slip agents, surface modifiers, thixotropic agents, thixotropic aids, silane coupling agents, polyhydric phenol compounds, etc. may include

[Films, color filters, black matrices, liquid crystal displays and solid-state imaging devices]
A patterned film 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 color filters, black matrices, and the like. That is, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. Moreover, a black matrix can be obtained by forming a pattern using a photosensitive resin composition containing a light shielding agent. Then, a liquid crystal display device and a solid-state imaging device having color filters and a black matrix can be manufactured.
A typical procedure for forming a pattern will be described.

(Formation of photosensitive resin film)
For example, a photosensitive resin film is first obtained by applying the above photosensitive resin composition onto an arbitrary substrate and drying it as necessary.

The substrate to which the composition is applied is not particularly limited. Examples thereof include glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, and copper-clad laminates.
The substrate may be an unprocessed substrate or a substrate having electrodes or elements formed thereon. It may be surface-treated to improve adhesion.

The method of applying the photosensitive resin composition is not particularly limited. It can be applied by spin coating using a spinner, spray coating using a spray coater, immersion, printing, roll coating, inkjet method, or the like.

Drying of the photosensitive resin composition coated on the substrate is typically performed by heat treatment using a hot plate, hot air, an oven, or the like. The heating temperature is usually 80-140°C, preferably 90-120°C. 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. 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 exposing the photosensitive resin film to actinic rays through a suitable photomask.

Actinic rays include, for example, X-rays, electron beams, ultraviolet rays, and visible rays. Light with a wavelength of 200 to 500 nm is preferable. From the viewpoint of pattern resolution and handleability, the light source is preferably g-line, h-line or i-line of a mercury lamp, and particularly preferably i-line. Also, two or more rays may be mixed and used. A contact aligner, mirror projection or stepper is preferred as the exposure device.
The amount of light for exposure may be appropriately adjusted depending on the amount of the photosensitive agent in the photosensitive resin film, and is, for example, about 100 to 500 mJ/cm ² .

After the exposure, the photosensitive resin film may be heated again as necessary (post-exposure heating: Post Exposure Bake). The temperature is, for example, 70-150°C, preferably 90-120°C. Also, the time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. Heating after exposure accelerates the reaction by radicals generated from the photoradical polymerization initiator, further accelerating the curing reaction.

(developing)
By developing the exposed photosensitive resin film with a suitable developer, a pattern can be obtained, and a patterned substrate 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 development process.

In the development step, development can be carried out using a suitable developer, for example, by a dipping method, a puddle method, a rotary spray method, or the like. By development, the exposed portion (in the case of a positive type) or the unexposed portion (in the case of a negative type) of the photosensitive resin film is eluted and removed to obtain a pattern.
Usable developer is not particularly limited. For example, an alkaline aqueous solution or an organic solvent can be used.

Specific examples of alkaline aqueous solutions include (i) inorganic alkaline aqueous solutions such as sodium hydroxide, sodium carbonate, sodium silicate and ammonia, (ii) organic amine aqueous solutions such as ethylamine, diethylamine, triethylamine and triethanolamine, and (iii) Examples include aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.
Since the polymer of the present embodiment has adjusted alkali solubility and excellent sensitivity, when using a strongly basic developer such as a TMAH (tetramethylammonium hydroxide) solution, the pattern after exposure and development can be formed as designed. can have the shape of

Specific examples of organic solvents include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether solvents such as propylene glycol monomethyl ether.
A water-soluble organic solvent such as methanol or ethanol, or a surfactant may be added to the developer.

In this embodiment, it is preferable to use an alkaline aqueous solution as the developer, and it is more preferable to use tetramethylammonium hydroxide, a sodium carbonate aqueous solution, or a potassium hydroxide aqueous solution.
The concentration of the alkaline aqueous solution is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.
Through the above steps, it is possible to obtain a pattern/manufacture a substrate with a pattern, and various treatments may be performed after development.

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

Alternatively, the obtained pattern may be heated to sufficiently harden it. The heating temperature is typically 150-400°C, preferably 160-300°C, more preferably 200-250°C. The heating time is not particularly limited, but is, for example, within the range of 15 to 300 minutes. This heat treatment can be performed using a hot plate, an oven, a heating oven in which a temperature program can be set, or the like. The atmospheric gas for the heat treatment may be air or an inert gas such as nitrogen or argon. Moreover, you may heat under pressure reduction.
FIG. 1 schematically shows an example of the structure of a liquid crystal display device and/or a solid-state imaging device having color filters and/or black matrices.

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

The substrate 10 is generally made of a material that transmits light, such as glass, polyester, polycarbonate, polyolefin, polysulfone, or a cyclic olefin polymer. The substrate 10 may be subjected to corona discharge treatment, ozone treatment, chemical treatment, or the like, if necessary.
Substrate 10 is preferably composed of glass.
The black matrix 11 is composed of, for example, a cured photosensitive resin composition containing a light shielding agent.

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

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above can be adopted. Moreover, the present invention is not limited to the above-described embodiments, and includes modifications, improvements, etc. within the scope of achieving the object of the present invention.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be employed within the scope that does not impair the effects of the present invention.

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

The compounds used in Examples may be indicated by the following abbreviations or trade names.
・MAN: maleic anhydride ・NB: 2-norbornene ・MEK: methyl ethyl ketone ・PEMP: pentaerythritol tetrakis (3-mercaptopropionate)
・HEMA: 2-hydroxyethyl methacrylate ・GMA: glycidyl methacrylate

<Synthesis of precursor polymer>
[Synthesis Example 1]
(Synthesis of precursor polymer A)
602.56 g of a 75% toluene solution of 2-norbornene (451.92 g as NB, 4.8 mol), maleic anhydride (MAN, 470.69 g, 4 .8 mol) and 2238.50 g of methyl ethyl ketone (MEK) were added, stirred and dissolved. Then, after removing dissolved oxygen in the system by nitrogen bubbling, it is heated, and when the internal temperature reaches 80 ° C., dimethyl 2,2′-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, trade name: 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 over 1 hour. After that, the mixture was further reacted at 80° C. for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was added dropwise to 3686.4 g of methanol to precipitate a white solid. The resulting 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 comprising structural units derived from 2-norbornene and structural units derived from maleic anhydride ( 908.1 g of precursor polymer A) were obtained.
As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 3,500, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.0. was 52.
The amount of sulfur in the obtained precursor polymer A was confirmed by elemental analysis by flask combustion and ion chromatography, and the presence of elemental sulfur in raw material polymer 1 was confirmed. In addition, the GPC measurement of the reaction solution did not show a single peak of ^PEMP and no unreacted PEMP remained. It was confirmed.

[Synthesis Example 2]
(Synthesis of precursor polymer B)
799.1 g of a polymer (precursor polymer B) was obtained in the same manner as in Synthesis Example 1 except that pentaerythritol tetrakis(3-mercaptopropionate) (PEMP) was not used.
The obtained polymer was measured by gel permeation chromatography (GPC) and found to have a weight average molecular weight Mw of 11,700 and a polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) of 1.0. was 90. Table 1 shows the results.

(Synthesis of polymer)
[Synthesis Example 3]
(Synthesis of polymer A)
Polymer A was synthesized by ring-opening the MAN unit of precursor polymer A with a monofunctional (meth)acrylic compound (HEMA) and then reacting it with an epoxy group-containing (meth)acrylic compound (GMA). Details will be described below.
First, 112.76 g of MEK was added to 60 g of precursor polymer A (0.312 mol in terms of MAN) to prepare a solution. To this solution was then added 81.2 g (0.624 mol) of HEMA, followed by 6.0 g (0.059 mol) of triethylamine and 0.30 g of 4-dimethylaminopyridine (DMAP, 0.0025 mol). ) was added and reacted at a temperature of 70° C. for 16 hours. After that, 44.4 g (0.312 mol) of GMA was added and reacted at a temperature of 70° C. for 8 hours to prepare a reaction solution.
The prepared reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. After that, polymer A was purified by the following procedure.
• The polymer was reprecipitated with an excess amount of water.
- The operation of washing the polymer solid obtained by reprecipitation with an excessive amount of water was repeated twice.
• The resulting reaction product was dried at 40°C for 16 hours.
As described above, the structural unit derived from maleic anhydride in precursor polymer A was ring-opened with HEMA to obtain polymer A, which was reacted with GMA.
GPC measurement of polymer A confirmed disappearance of the peak of the monofunctional (meth)acrylic compound used and the peak of the epoxy group-containing (meth)acrylic compound. Thus, it was confirmed that the obtained polymer A contained neither an unreacted (meth)acrylic compound nor an epoxy group-containing (meth)acrylic compound.
¹ H-NMR measurement confirmed that Polymer A had a HEMA-opened structure and a GMA-reacted structure.
Table 2 shows the results.

[Synthesis Example 4]
(Synthesis of Polymer B)
Polymer B was synthesized in the same manner as in Synthesis Example 3 except that precursor polymer B was used.
Table 2 shows the results.

[Synthesis Example 5]
(Synthesis of Polymer C)
Polymer C was synthesized in the same manner as in Synthesis Example 3, except that the amount of GMA was halved.
As a result of measurement by ¹ H-NMR, the unreacted carboxylic acid contained in Polymer C was found to be 17 mol %.
Table 2 shows the results.

[Example 1, Comparative Examples 1 and 2]
(Preparation of polymer solution)
100 parts by mass of the polymers obtained in Synthesis Examples 3 to 5 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a polymer solution 1 having a solid concentration of 30% by mass.

(Preparation of photosensitive resin composition)
A photosensitive resin composition was prepared by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) such that the total solid concentration was 30% by mass.
- Solid content in the polymer solution (each polymer): 100 parts by mass - Polyfunctional acrylate (dipentaerythritol hexaacrylate) (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH): 50 parts by mass - Photoinitiator ( BASF Corporation, Irgacure OXE01): 5 parts by mass Adhesion aid (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass Surfactant (DIC Corporation, F-556): 0.5 mass Part The obtained photosensitive resin composition was filtered through a PTFE membrane filter Millex-LS (manufactured by Merck Millipore) as necessary to remove insoluble matter.

<Evaluation method>
The polymers synthesized in Synthesis Examples and the photosensitive resin compositions obtained in Examples and Comparative Examples were evaluated as follows.

(Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (PDI))
Weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (PDI: Mw/Mn) are obtained from a standard polystyrene (PS) calibration curve obtained by GPC measurement, and polystyrene conversion values are used. The measurement conditions are as follows. Table 1 shows the results.
Gel permeation chromatography device HLC-8320GPC manufactured by Tosoh Corporation
Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation
Detector: RI detector for liquid chromatogram Measurement temperature: 40°C
Solvent: THF
Sample concentration: 2.0 mg/ml

[transparency]
The photosensitive resin composition was coated on a Corning glass substrate having a size of 100 mm in length and 100 mm in width, dried at 100° C. for 120 seconds, and applied with a g + h + i line mask aligner (PLA-501F (manufactured by Canon Inc.). An ultra-high pressure mercury lamp)) was used to expose the entire surface to the g+h+i line so that the integrated amount of light was 100 mJ/cm 2 , and a resin film having a thickness of about 3.0 μm was obtained. For a cured film obtained by heating this resin film at 230 ° C. for 1 hour in an air atmosphere, the light transmittance at wavelengths of 550 nm and 400 nm was evaluated with an ultraviolet-visible spectrophotometer, and the obtained transmittance was measured at each wavelength. The transparency of the cured film was defined as the transparency.

[chemical resistance]
A photosensitive resin composition is spin-coated on a 3-inch silicon wafer (500 to 2500 rpm) and pre-baked on a hot plate at 100° C. for 120 seconds to form a resin having a thickness of about 3.0 μm. A membrane was obtained. Next, the entire surface of the resin film was exposed to g+h+i rays using a g+h+i-ray mask aligner (manufactured by Canon Inc., PLA-501F (ultra-high pressure mercury lamp)) so that the integrated light amount was 100 mJ/cm. Further, the resin film was heat-treated in an oven at 230° C. for 1 hour. The cured film thus obtained was immersed in a mixture of monoethanolamine and dimethylsulfoxide (=7:3) at 70° C. for 1 minute, and then rinsed with pure water for 30 seconds.

[Heat-resistant]
For the cured film, the temperature was raised at 10 ° C./min with a Tg-DTA device (TG/DTA6200, manufactured by Seiko Instruments Inc.) to obtain a 1% thermal weight loss temperature (Td1) and a 5% thermal weight loss temperature (Td5). was measured.

From the results of Table 3, the photosensitive resin composition of the present embodiment is excellent in curability and heat resistance, and is a cured product with excellent durability such as transparency and solvent resistance, in other words, an excellent balance of these properties. It has become clear that a cured product can be provided.

10 substrate 11 black matrix 12 color filter 13 protective film 14 transparent electrode layer

Claims (6)

a polymer containing structural units (1) to (5) represented by the following general formulas (1) to (5);
a polymerization initiator;
including
A photosensitive resin composition in which a cured film having a thickness of 3 μm obtained by heating at 230° C. for 60 minutes satisfies the following characteristics (a) and (b).
(a) The light transmittance at a wavelength of 400 nm and the light transmittance at a wavelength of 550 nm are 95% or more.
(b) The film thickness change rate represented by the following formula after being immersed in a mixed solvent of monoethanolamine/DMSO=70/30 (weight ratio) at 70° C. for 1 minute is 5.0% or less.
(formula)
[(film thickness after immersion at 70 ° C. for 1 minute - film thickness before immersion) / film thickness before immersion] × 100

(In general formula (2), 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, It represents a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and the alkyl group for Q and any carbon atom of the alkylene group for X may combine to form a ring.
In general formula (3), ^RA is a group containing one or more (meth)acryloyl groups.
In general formula (5), 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. ) In the polymer, when the total of the structural units (1) to (5) is 100 mol%, the structural unit (1) is 0 to 5 mol% and the structural unit (4) is 0 to 5 mol%, 2. The photosensitive resin composition according to claim 1, wherein the total amount of structural units (2), (3) and (5) is 90 to 100 mol %. 3. The photosensitive resin composition according to claim 1, wherein the cured film has a 1% weight loss temperature (Td1) of 270° C. or higher and a 5% weight loss temperature (Td5) of 330° C. or higher. The photosensitive resin composition according to any one of claims 1 to 3, wherein the polymer is bonded via a thioether group derived from at least one thiol group of a thiol group-containing compound having two or more functionalities. The photosensitive resin composition according to any one of claims 1 to 4, further comprising a polyfunctional (meth)acrylic compound. A cured film comprising the photosensitive resin composition according to any one of claims 1 to 5.

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