TWI669319B - Resin composition, photosensitive resin composition, resin cured film, and image display element - Google Patents

Abstract

Provided is a resin composition suitable as a material of a photosensitive resin composition, which can obtain a resin cured film having excellent developability and has excellent storage stability.
The resin composition of the present invention comprises: a polymer (A) having an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbons; and a compound containing a hydroxyl group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbons ( B) contains 0.001 to 1.0 parts by mass of the compound (B) with respect to 100 parts by mass of the total of the polymer (A) and the compound (B). The compound (B) is preferably composed of any one or more selected from the following alcohols and reaction products of the alcohols and polybasic acid anhydrides, and the aforementioned alcohols are selected from the group consisting of dicyclopentenol, dicyclopentanol, isofluorene Alcohol, amantadine.

Description

Resin composition, photosensitive resin composition, resin cured film, and image display element

The present invention relates to a resin composition, a photosensitive resin composition, a resin cured film, and an image display device including the same.
This application claims priority based on Japanese Patent Application No. 2017-245166 filed in Japan on December 21, 2017, and incorporates this content in this application.

In recent years, from the viewpoint of saving resources and energy, in various fields such as coating, printing, coatings, and adhesives, the photosensitive resin composition can be cured by active energy rays such as ultraviolet rays and electron rays. It has been widely used. In the field of electronic materials such as printed wiring boards, photosensitive resin composition systems are used in solder resists, color filter resists, and the like.

A color filter generally includes a transparent substrate such as a glass substrate, red (R), green (G), and blue (B) pixels formed on the transparent substrate, and black formed at a pixel boundary. Matrix and protective film formed on pixels and black matrix. A color filter is generally manufactured by sequentially forming a black matrix, each pixel, and a protective film on a transparent substrate.

As a method of forming each pixel and the black matrix, various manufacturing methods have been proposed. Nowadays, a photolithography method using a photosensitive resin composition as a resist and repeated coating, exposure, development, and baking has become a mainstream method for forming each pixel and a black matrix. . Each pixel and black matrix formed by this method has excellent light resistance and heat resistance, and has fewer defects such as pinholes.

Generally, a photosensitive resin composition used in a photolithography method includes a resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. The photosensitive resin composition used in the photolithography method must have developability.

Conventionally, as a resin used in a photosensitive resin composition, a resin as a copolymer has been proposed, which is an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, a radical polymerizable compound having an epoxy group, Copolymers of other radically polymerizable compounds (see, for example, Patent Document 1).
In addition, as a resin used in the photosensitive resin composition, a resin composition has been proposed, which includes a copolymer which is synthesized using glycidyl (meth) acrylate but does not have an acid group, and is polymerized. A copolymer having a weight average molecular weight of styrene conversion of 1,000 to 50,000; a copolymer having an acid group and a weight average molecular weight of polystyrene conversion of 1,000 to 50,000 (refer to, for example, Patent Document 2).
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 06-043643
[Patent Document 2] Japanese Patent Laid-Open No. 2015-222279

[Problems to be Solved by the Invention]

However, the storage stability of the conventional photosensitive resin composition is insufficient.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition suitable as a material of a photosensitive resin composition, which can obtain a resin hardened film having excellent developability and has excellent Storage stability.
Another object of the present invention is to provide a photosensitive resin composition containing the resin composition of the present invention, capable of obtaining a resin cured film having excellent developability, and having excellent storage stability.
Moreover, the subject of this invention is providing the resin hardened film which is a hardened | cured material of the photosensitive resin composition of this invention, and the image display element provided with this.

[Means for solving problems]

In order to solve the above problems, the present inventors have conducted intensive studies.
As a result, it has been found that if the resin composition is set to contain a polymer (A) having a bridged cyclic hydrocarbon group having an acid group and a carbon number of 10 to 20 in a specific ratio, and a hydroxyl group or an acid group having a carbon number of 10 to 20, The compound (B) of a bridged cyclic hydrocarbon group can be considered in the present invention.
That is, this invention relates to the following matters.

[1]. A resin composition characterized by containing a polymer (A) having an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and a bridged ring type containing a hydroxyl group or an acid group with 10 to 20 carbon atoms The hydrocarbon-based compound (B) contains 0.001 to 1.0 part by mass of the compound (B) with respect to 100 parts by mass of the total of the polymer (A) and the compound (B).
[2]. The resin composition according to [1], wherein the compound (B) is any one or more selected from the following alcohols and reaction products of the alcohol and a polybasic acid anhydride, and the alcohol is selected from the group consisting of two Cyclopentenol, dicyclopentanol, isoamyl alcohol, amantadine.

[3]. The resin composition according to [1] or [2], wherein the polymer (A) has an unsaturated bond.
[4]. The resin composition according to any one of [1] to [3], further comprising a solvent (C).
[5]. The resin composition according to any one of [1] to [4], further comprising a reactive diluent (D).

[6] A photosensitive resin composition comprising the resin composition according to any one of [1] to [5] and a photopolymerization initiator (E).
[7]. The photosensitive resin composition according to [6], wherein the photopolymerization initiator (E) is one or both of an acetophenone-based and an oxime ester-based.
[8]. The photosensitive resin composition according to [6] or [7], further comprising a colorant (F).
[9]. The photosensitive resin composition according to [8], wherein the colorant (F) contains a dye.
[10]. The photosensitive resin composition according to [9], wherein the colorant (F) is one or both of anthraquinone-based dye and xanthene-based dye.

[11]. A resin cured film, characterized in that it is a cured product of the photosensitive resin composition according to any one of [7] to [10].
[12]. An image display element comprising the resin cured film according to [11].

[Effect of the invention]

The resin composition of the present invention comprises a polymer (A) having an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and a compound containing a hydroxyl group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms ( B) contains 0.001 to 1.0 parts by mass of the compound (B) with respect to 100 parts by mass of the total of the polymer (A) and the compound (B). Therefore, the resin composition of the present invention is a material suitable as a photosensitive resin composition, which can obtain a resin hardened film having excellent developability and has excellent storage stability.
Since the photosensitive resin composition of this invention contains the resin composition of this invention, the resin hardened film which has the outstanding developability can be obtained, and it has the outstanding storage stability.

[Best Mode for Implementing Invention]

Hereinafter, the resin composition, the photosensitive resin composition, the resin cured film, and the image display element of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below.

[1. Resin composition]
The resin composition of the present invention contains a polymer (A) having an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbons, and a compound (B) containing a hydroxyl group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbons. .
The compound (B) has a function of improving the storage stability of the polymer (A), which has not been known before. Therefore, in order to improve the storage stability of the polymer (A), an operation of adding the component (B) to the polymer (A) has not been performed conventionally.
As a result of intensive research in order to solve the above-mentioned problems, the present inventors found that by setting the resin composition as follows: "Compared with 100 parts by mass of the polymer (A) and the compound (B) in total, the compound contains 0.001 to 1.0 parts by mass (B) ", so that a resin composition can be obtained, which can obtain a resin hardened film having excellent developability and excellent storage stability, and thus the present invention has been considered.

(Polymer (A))
The polymer (A) is not particularly limited as long as it is a cross-linking cyclic hydrocarbon group having an acid group and a carbon number of 10 to 20 in the molecule. The polymer (A) is preferably a polymerization unit having an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms.
Since the polymer (A) has an acid group in the molecule, the resin hardened film composed of the hardened product of the photosensitive resin composition containing the polymer (A) will have good alkali developability. In addition, since the polymer (A) is a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms in the molecule, a resin cured film composed of a cured product of the photosensitive resin composition containing the polymer (A) has heat resistance. For good.

Examples of the acid group of the polymer (A) include a carboxyl group (-COOH), a sulfonic acid group (-SO ₃ H), and a phosphate group (-PO (OH) ₂ ). A carboxyl group is particularly preferred. When the acid group of the polymer (A) is a carboxyl group, a resin-hardened film composed of a cured product of the photosensitive resin composition containing the polymer (A) has better developability. The polymer (A) may have only one kind of acid group or two or more kinds of acid groups. The number of acid groups in each polymerized unit of the polymer (A) may be only one, or may be two or more.

The bridged cyclic hydrocarbon group having 10 to 20 carbon atoms contained in the polymer (A) is a group equivalent to a residue after removing one hydrogen atom from the bridged cyclic hydrocarbon having 10 to 20 carbon atoms. Among the bridged cyclic hydrocarbon groups in the polymer (A), the structure of the bridged cyclic hydrocarbon is preferably a structure represented by the following formula (3) and / or formula (4), and specifically, an adamantane skeleton is mentioned , Norbornane skeleton. The bridged cyclic hydrocarbon group of the polymer (A) is preferably a group equivalent to removing a remaining portion of one hydrogen atom from the structure represented by the following formula (3) and / or formula (4).

(In formula (3), A ¹ and B ¹ respectively represent a linear or branched alkylene (including a cyclic formula), R ⁴ represents a hydrogen atom or a methyl group, A ¹ and B ¹ may be the same or different, and A ^1. The branches of B ¹ can be connected to each other to form a ring);

(In formula (4), A ² , B ² , and L respectively represent a linear or branched alkylene (including a cyclic formula), R ⁵ represents a hydrogen atom or a methyl group, and A ² , B ² , and L may be the same or Differently, the branches of A ² , B ² , and L can be connected to each other to form a ring).

The acid value (JIS K6901 5.3) of the polymer (A) is not particularly limited. When the polymer (A) is used as a material of the photosensitive resin composition, the acid value of the polymer (A) is preferably in the range of 10 to 300 KOHmg / g, and more preferably in the range of 20 to 200 KOHmg / g.

The weight average molecular weight (Mw) of the polymer (A) is preferably 1,000 to 50,000, and more preferably 3,000 to 40,000. When the weight average molecular weight of the polymer (A) is 1,000 or more, if a resin cured film composed of a cured product of the photosensitive resin composition containing the polymer (A) is developed, pattern defects are less likely to occur, and Get better developability. If the weight average molecular weight of the polymer (A) is 50,000 or less, the development time of the resin cured film composed of the cured product of the photosensitive resin composition containing the polymer (A) will not be excessively long. , And is practical.

The "weight average molecular weight (Mw)" as used in this specification means the meaning of the weight average molecular weight equivalent to standard polystyrene measured by gel permeation chromatography (GPC) under the following conditions.
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Corporation)
Column temperature: 40 ℃
Sample: 0.2% tetrahydrofuran solution of copolymer. Development solvent: tetrahydrofuran detector: differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko Corporation)
Flow rate: 1mL / min

The polymer (A) may have an unsaturated bond. When the polymer (A) has an unsaturated bond, the photosensitive resin composition containing the polymer (A) becomes a highly sensitive one. The polymer (A) having an unsaturated bond is preferably a polymer (II) or a polymer (III) described later.
In the polymer (A) having an unsaturated bond, the unsaturated bond equivalent is preferably in a range of 100 to 4,000 g / mol, and more preferably in a range of 300 to 2,000 g / mol.

The "unsaturated bond equivalent" in this specification refers to the mass of the polymer per 1 mol of the unsaturated bond of the polymer. The unsaturated bond equivalent can be obtained by dividing the mass of the polymer by the mole number of unsaturated bonds of the polymer contained therein (g / mol).
In the present specification, the unsaturated bond equivalent is a theoretical value obtained by calculation from a raw material used when producing a polymer and a loading amount of a raw material used to introduce an unsaturated bond.

In the polymer (A) having an unsaturated bond, if the unsaturated bond equivalent is 100 g / mol or more, a resin cured film composed of a cured product of the photosensitive resin composition containing the polymer (A) will be more effective. Improve heat resistance and developability one layer at a time. In the polymer (A) having an unsaturated bond, if the unsaturated bond equivalent is 4,000 g / mol or less, a resin cured film composed of a cured product of the photosensitive resin composition containing the polymer (A) will become Higher sensitivity.

The polymer (A) is specifically preferably the following polymer (I), polymer (II), or polymer (III).

Polymer (I): A copolymer having a polymerization unit including a constituent component derived from a monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and an unsaturated acid monomer The constituents of the body (a2) and constituents derived from other monomers (a3) used as desired.
Polymer (II): A denatured polymer that is branched from the polymerization unit of the copolymer of (I), and an unsaturated monomer derived from a functional group that reacts with an acid group is introduced as an unsaturated bond ( a4).
Polymer (III): A denatured polymer which is branched from the polymerization unit of a copolymer having the following polymerization units, and introduces, as unsaturated bonds, constituents derived from unsaturated monobasic acid (a5) and as The acid group is derived from a polybasic acid or a constituent component of the anhydride (a6), and the aforementioned polymerization unit includes: the constituent component derived from the above (a1), the constituent component derived from the above (a4), and a source derived from the desired use (A3).

(Polymer (I))
The polymer (I) is a copolymer having a polymerization unit including a constituent component derived from a monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and an unsaturated acid monomer. The constituents of the body (a2) and constituents derived from other monomers (a3) used as desired.

"Bridged cyclic hydrocarbon group monomer (a1) with 10 to 20 carbon atoms"
The monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and used as a raw material of the polymer (I) and constituting the polymer (I) is preferably a bridged ring having 10 to 20 carbon atoms. (Meth) acrylates of the formula hydrocarbyl.
The "(meth) acrylate" in this specification means acrylate, methacrylate, or both.

The monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms is also preferably a (meth) acrylate having a structure represented by the above formula (3) and / or formula (4), more preferably Adamantane (meth) acrylate and / or (meth) acrylate having a structure represented by the following formula (5).

(In formula (5), R ⁶ to R ⁸ each independently represent a hydrogen atom or a methyl group, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group, or a saturated or unsaturated ring formed by being connected to each other, * Represents a bond to (meth) acryloxy (CH ₂ = CHCOO- or CH ₂ = C (CH ₃ ) COO-).

In the structure represented by formula (5), R ⁶ to R ^{8 are} preferably hydrogen atoms, and R ⁹ and R ^{10 are} preferably connected to each other to form a saturated or unsaturated 5-membered ring or 6-membered ring.

Specific examples of the (meth) acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms are selected from the group consisting of dicyclopentenyl (meth) acrylate, dicyclopentyl (meth) acrylate, and (methyl) Any one or two or more kinds of (meth) acrylic acid isoamyl acrylate and adamantane (meth) acrylate, preferably dicyclopentanyl methacrylate. When the polymer (I) is a polymer having a constituent component derived from dicyclopentyl methacrylate, a resin cured film composed of a cured product of the photosensitive resin composition containing the polymer (I) is thermally decomposed. Properties and heat yellowing resistance will become good.

"Unsaturated acid monomer (a2)"
The unsaturated acid monomer (a2) used as a raw material of the polymer (I) and constituting the polymer (I) has a polymerizable unsaturated bond and an acid group. If the polymer (I) is a polymer having a constituent component derived from an unsaturated acid monomer (a2), a resin cured film composed of a cured product of the photosensitive resin composition containing the polymer (I), because The acid group derived from the unsaturated acid monomer (a2) can obtain good developability.
The unsaturated acid monomer (a2) may be any monomer having a polymerizable unsaturated bond and an acid group, and examples thereof include an unsaturated carboxylic acid or the acid anhydride, an unsaturated sulfonic acid, and an unsaturated phosphonic acid. Any one or more monomers.

Specifically, examples of the unsaturated acid monomer (a2) include (meth) acrylic acid, α-bromo (meth) acrylic acid, β-furyl (meth) acrylic acid, crotonic acid, propionic acid, and cinnamon Acid, α-cyanocinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, Unsaturated carboxylic acids such as citraconic acid and citraconic anhydride, or the anhydrides; Saturated sulfonic acid; Unsaturated phosphonic acid, such as ethylene phosphonic acid.

Among these, as the unsaturated acid monomer (a2), since the polymer (I) having a carboxyl group can be obtained, an unsaturated carboxylic acid or the acid anhydride is preferred, and (meth) acrylic acid is particularly preferred.
The "(meth) acrylfluorenyl" in this specification refers to acrylamyl, methacrylfluorenyl, or both.

The polymer (I) may be a copolymer containing a constituent component derived from a monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a constituent component derived from an unsaturated acid monomer (a2). It may be a copolymer containing constituent components derived from the monomers (a1) and (a2) described above, and one or two or more constituent components derived from other monomers (a3).

"Other monomer (a3)"
The other monomer (a3) used as a raw material of the polymer (I) and constituting the polymer (I) is not the following monomer: "One of the bridged cyclic hydrocarbon groups having 10 to 20 carbon atoms Monomer (a1), unsaturated acid monomer (a2), unsaturated monomer (a4) having a functional group that reacts with an acid group, unsaturated monoacid (a5), polyacid, or the acid anhydride (a6) ", Specific examples include: styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, and p-chlorobenzene Ethylene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetamidostyrene, etc. Aromatic vinyl compounds

Norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, etc. Cyclic olefins with norbornene structure; butadiene, isoprene, chloroprene and other dienes;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid sec-butyl ester, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, (formyl) Base) cyclohexyl acrylate, methyl cyclohexyl (meth) acrylate, ethyl cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, (meth) Norbornyl acrylate, 5-methyl norbornyl (meth) acrylate, 5-ethyl norbornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1 (meth) acrylate 1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, 3- (N, N-dimethylamino) propyl esters (meth) acrylates without aromatic rings;

Benzyl (meth) acrylate, rosin (meth) acrylate, triphenylmethyl (meth) acrylate, phenyl (meth) acrylate, isophenylpropyl (meth) acrylate, (meth) acrylic acid 4-phenoxyphenyl ester, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, biphenoxyethyl (meth) acrylate (Meth) acrylates having aromatic rings, such as naphthyl (meth) acrylate, anthracene (meth) acrylate, etc .;

Ammonium (meth) acrylate, N, N-dimethylammonium (meth) acrylate, N, N-diethylammonium (meth) acrylate, N, N-dipropyl (meth) acrylate (Meth) acrylamide (meth) acrylamide (N, N-di-isopropylamidamine (meth) acrylate, anthrylamine (meth) acrylate), aniline (meth) acrylate, (meth) acrylic acid Vinyl compounds such as acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinylidene fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene, etc .; diethyl citraconic acid Unsaturated dicarboxylic acid diesters such as esters, diethyl maleate, diethyl fumarate, diethyl iconate, etc .; N-phenylmaleimide, N-cyclohexylmaleimide , N-lauryl maleimide, N- (4-hydroxyphenyl) maleimide, and other monomaleimide and the like.

Among these, the other monomer (a3) is preferably one or more selected from the group consisting of an aromatic vinyl compound, a cyclic olefin having a norbornene structure, and an aromatic (meth) acrylate. .
When the polymer (I) is a polymer having a constituent component derived from an aromatic vinyl compound, a resin cured film composed of a cured product of the photosensitive resin composition containing the polymer (I) will have a good Thermal decomposition and pigment dispersibility. When the polymer (I) is a polymer having a constituent component derived from a cyclic olefin having a norbornene structure, the resin composed of a cured product of the photosensitive resin composition containing the polymer (I) is cured. The film will have good thermal decomposition resistance, thermal yellowing resistance and pigment dispersibility. When the polymer (I) is a polymer having a constituent component derived from an aromatic (meth) acrylate, the resin is composed of a cured product of a photosensitive resin composition containing the polymer (I). The cured film will have good pigment dispersibility.

The content of the constituents derived from the above-mentioned monomers (a1), (a2), and (a3) in the polymer (I) is different from the monomers (a1) (a2) used as the raw material of the polymer (I) The ratio of (a3) is considered the same.
In the polymer (I), the content of the constituent components derived from the bridged cyclic hydrocarbon-based monomer (a1) having 10 to 20 carbon atoms is preferably 1 to 90 mole%, and more preferably 2 to 80 mole%. , More preferably 3 to 70 mole%. When the content of the component derived from the monomer (a1) is in the above range, the resin cured film composed of the cured product of the photosensitive resin composition containing the polymer (I) will have better heat resistance.

In the polymer (I), the content of the constituents derived from the unsaturated acid monomer (a2) is preferably 10 to 99 mol%, more preferably 15 to 98 mol%, and more preferably 20 to 97. Mohr%. When the content of the component derived from the monomer (a2) is within the above range, when the resin-hardened film composed of the cured product of the photosensitive resin composition containing the polymer (I) is subjected to alkali development, the development speed will be Appropriate and more developable.

In the polymer (I), the content of the constituent components derived from other monomers (a3) is preferably 0 to 80 mole%, more preferably 5 to 70 mole%, and more preferably 10 to 65 mole%. ear%. By containing 80 mol% or less of the component derived from the monomer (a3), the pigment dispersibility of the polymer (I) can be appropriately improved, and the photosensitive resin composition containing the polymer (I) can be hardened. The properties of the resin-cured film made of materials such as heat resistance.

(Production method of polymer (I))
The polymer (I) can be, for example, a monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, an unsaturated acid monomer (a2), and other monomers (a3) used as required. It is produced by a method of copolymerization by a conventionally known radical polymerization method.
The copolymerization reaction for producing the polymer (I) can be performed in the presence of a solvent. For example, the above monomers (a1) and (a2) and (a3) used as needed are dissolved in a solvent, a polymerization initiator is added to the obtained solution, and a copolymerization reaction is performed at 50 to 130 ° C for 1 to A 20-hour method whereby polymer (I) can be produced.

The solvent (polymerization solvent) used in producing the polymer (I) is not particularly limited as long as it is inert in the polymerization reaction, and examples thereof include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono Methyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, two (Poly) alkylene glycol monoalkyl ethers such as propylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether;

(Poly) alkylene glycol mono, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Alkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, cyclic Ketones such as hexanone, 2-heptanone, 3-heptanone;

Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate Esters, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3- Methyl methyl butyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, acetic acid n-propyl ester, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, butyrate n -Propyl ester, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-oxo Esters such as ethyl butyrate;

Aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and other carboxylic acid amines and the like. These solvents can be used alone or in combination of two or more.
Among these polymerization solvents, glycol ether solvents are preferred, and (poly) alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetic acid are particularly preferred. (Poly) alkylene glycol monoalkyl ether acetates such as esters.

The amount of the polymerization solvent used in the production of the polymer (I) is not particularly limited, and it is generally 30 to 1,000 parts by mass, preferably 50 to 1,000 parts by mass relative to the total amount of the monomers as raw materials. 800 parts by mass. By using the solvent in an amount of 1,000 parts by mass or less, a decrease in the molecular weight of the polymer (I) due to a chain transfer effect can be suppressed, and the viscosity of the polymer (I) can be controlled within an appropriate range. In addition, by using the solvent in an amount of 30 parts by mass or more, abnormal polymerization reaction can be prevented, the polymerization reaction can proceed stably, and coloration or gelation of the polymer (I) can be prevented.

In the copolymerization reaction for producing the polymer (I), as the polymerization initiator used, for example, azobisisobutyronitrile, azobisisovaleronitrile, benzamidine peroxide, t- Butylperoxy-2-ethylhexanoate and the like are not particularly limited. These polymerization initiators can be used alone or in combination of two or more.
The amount of the polymerization initiator used is generally 0.5 to 20 parts by mass, and preferably 1.0 to 10 parts by mass, with respect to 100 parts by mass of the total amount of the charged monomers.

(Polymer (II))
The polymer (II) is a denatured polymer, which is branched into the polymerization unit of the copolymer of the polymer (I), and an unsaturated bond derived from an unsaturated monomer derived from a functional group that reacts with an acid group is introduced. Body (a4). In the polymer (II), since an unsaturated bond is introduced into a branch of a polymerization unit as a copolymer of the polymer (I), the photosensitive resin composition containing the polymer (II) becomes a highly sensitive person.

"Unsaturated monomer (a4) having a functional group reactive with an acid group"
The unsaturated monomer (a4) having a functional group reactive with an acid group, which is used as a raw material of the polymer (II) and becomes a constituent component of the polymer (II), may be only one kind, or two or more kinds, An unsaturated compound having a functional group that reacts with an acid group such as an epoxy group, a hydroxyl group, an amine group, or a vinyl ether group is preferred.

Specific examples of the unsaturated monomer (a4) having a functional group that reacts with an acid group include glycidyl (meth) acrylate, and (meth) acrylic acid having alicyclic epoxy groups 3,4 -Epoxy cyclohexyl methyl ester and its lactone adducts (for example, Cyclomer A200, M100 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxy cyclohexylmethyl-3 ', 4'-cyclo Mono (meth) acrylate of oxycyclohexane carboxylate, epoxide of dicyclopentenyl (meth) acrylate, epoxide of dicyclopentenyloxyethyl (meth) acrylate, etc. Free radical polymerizable monomers with epoxy groups; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) 6-hydroxyhexyl acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloxy-2-hydroxypropyl phthalate, allyl alcohol Radical polymerizable monomers having a hydroxyl group, etc .; Radical polymerizable monomers having an amine group, such as 4-aminostyrene; 2-ethyleneoxyethoxyethyl (meth) acrylate, etc. having ethylene Radical polymerizable monomer such as an ether group.

Among such unsaturated monomers (a4) having a functional group that reacts with an acid group, a radically polymerizable monomer having an epoxy group is preferably used, and glycidyl (meth) acrylate is particularly preferred. . As the unsaturated monomer (a4) having a functional group that reacts with an acid group, if a radically polymerizable monomer having an epoxy group is used, when producing the polymer (II), it is used as a source of the acid group. The reaction from the constituents of the unsaturated acid monomer (a2) can easily introduce an unsaturated bond into the branch chain of the copolymer as the polymer (I).

The content of the constituents derived from the monomers (a1) (a2) (a3) (a4) in the polymer (II) is the monomer (a1) used separately from the polymer (II) as a raw material The ratios of (a2) (a3) (a4) are considered the same.
The preferable range of the content of the constituents derived from the above-mentioned monomers (a1) (a2) (a3) in the polymer (II) is the same as that derived from the above-mentioned monomers (a1) ( a2) (a3) The content of the constituent components is the same.

In the polymer (II), the content of the constituent component of the unsaturated monomer (a4) derived from a functional group that reacts with an acid group is preferably 1 to 95 mole%, and more preferably 3 to 75 mole. %, More preferably 5 to 55 mole%. When the content of the component derived from the monomer (a4) is within the above range, the content of the component derived from the monomers (a1) (a2) (a3) can be ensured, and the content of the polymer ( II) Sensitivity of the photosensitive resin composition.

(Production method of polymer (II))
The polymer (II) can be a copolymer of the polymer (I) and an unsaturated monomer (a4) having a functional group that reacts with an acid group, and can be reacted by a conventionally known method to make the polymerizable An unsaturated bond is introduced into a branch of a copolymer to form a denatured polymer.
Specifically, for example, a copolymer as a polymer (I), an unsaturated monomer (a4) having a functional group that reacts with an acid group, a polymerization inhibitor, and a catalyst are added to the reaction solvent at 50 to 150 ° C. (Preferably 80 to 130 ° C.) A method for subjecting the polymer to a denaturation reaction, whereby a polymer (II) can be produced.
The denaturation reaction for producing the polymer (II) does not have any particular problem even if it includes a solvent used in the copolymerization reaction for producing the polymer (I). Therefore, after the completion of the copolymerization reaction for producing the polymer (I), a denaturation reaction for producing the polymer (II) can be performed without removing the solvent.

In the production of the polymer (II), the polymerization inhibitor used to prevent gelation is not particularly limited, and examples thereof include hydroquinone, methylhydroquinone, and hydroquinone monomethyl ether.
The catalyst used in producing the polymer (II) is not particularly limited, and examples thereof include a tertiary amine such as triethylamine, and a quaternary ammonium such as triethylbenzyl ammonium chloride. Salts, phosphorus compounds like triphenylphosphine, chelate compounds of chromium, and the like.

(Polymer (III))
Polymer (III) is a denatured polymer, which is branched from the polymerization unit of a copolymer having the following polymerization units, and introduces, as unsaturated bonds, constituents derived from unsaturated monobasic acid (a5) and as The acid group is derived from a polybasic acid or a constituent component of the anhydride (a6), and the aforementioned polymerization unit includes a constituent component derived from a monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, The constituents of the unsaturated monomer (a4) which is a functional group that reacts with a group, and constituents derived from other monomers (a3) that are used as desired.

The polymer (III) includes copolymerization of the constituent components derived from the monomer (a1), the constituent components derived from (a4), and the constituent components derived from other monomers (a3) as desired. Since unsaturated chains are introduced into the branch of the material, the sensitivity of the photosensitive resin composition containing the polymer (III) is high. In addition, since the polymer (III) introduces acid groups into the above-mentioned branches, a resin cured film composed of a cured product of the photosensitive resin composition containing the polymer (III) will have good developability.

As the monomer (a1) (a3) used as a raw material of the polymer (III) and constituting the polymer (III), the monomer (a1) used as a constituent of the polymer (I) can be used. ) (a3) is the same monomer. In addition, as the monomer (a4) used as a raw material of the polymer (III) and constituting the polymer (III), the monomer (a4) used as a constituent of the polymer (II) can be used. Are the same monomer.

Among the monomers (a4) used as the constituent component of the polymer (III), the monomers (a4) used as the constituent component of the polymer (II) are preferably those having a ring. The radically polymerizable monomer of an oxygen group is particularly preferably a glycidyl (meth) acrylate. As the unsaturated monomer (a4) having a functional group that reacts with an acid group, if a radically polymerizable monomer having an epoxy group is used, it can be easily used as a precursor of the polymer (III) described later. The branched chain introduces unsaturated bonds and acid groups.

"Unsaturated Monobasic Acid (a5)"
The unsaturated monobasic acid (a5) used as a raw material of the polymer (III) and constituting the polymer (III) includes, for example, (meth) acrylic acid, α-bromo (meth) acrylic acid, and β- Unsaturation of furyl (meth) acrylic acid, crotonic acid, propynic acid, cinnamic acid, α-cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc. A carboxylic acid or the like can be used as an unsaturated acid monomer (a2).

"Polyacid or the anhydride (a6)"
Examples of the polybasic acid used as a raw material of the polymer (III) and constituting the polymer (III) or the anhydride (a6) include maleic acid, maleic anhydride, fumaric acid, itaconic acid, Unsaturated carboxylic acids such as itaconic anhydride, citraconic acid, citraconic anhydride or the like; 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, p-styrenesulfonic acid An unsaturated sulfonic acid such as an acid; an unsaturated polybasic acid exemplified as the unsaturated acid monomer (a2) such as an unsaturated phosphonic acid such as ethylene phosphonic acid; and the acid anhydride.

The polybasic acid or the anhydride (a6) serving as a constituent component of the polymer (III) may be an unsaturated polybasic acid having no polymerizability and the acid anhydride, a saturated polybasic acid, and the anhydride, and examples thereof include malonic acid and amber Acid, glutaric acid, adipic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl- Dinor acids such as 5-norbornene-2,3-dicarboxylic acid, phthalic acid, tribasic acids such as trimellitic acid, tetrabasic acids such as pyromite, and anhydrides thereof.
Among these, a dicarboxylic anhydride is preferably used as the polybasic acid or the acid anhydride (a6).

The content of the constituents of the polymer (III) derived from the above-mentioned monomers (a1) (a3) (a4), unsaturated monobasic acid (a5), polybasic acid, or the anhydride (a6) is the same as that of the polymer The proportions of the monomers (a1) (a3) (a4), unsaturated monoacids (a5), polybasic acids, or the acid anhydride (a6) used in the raw materials of (III) may be regarded as the same.

In the polymer (III), the content of the constituent components derived from the bridged cyclic hydrocarbon-based monomer (a1) having 10 to 20 carbon atoms is preferably 1 to 80 mole%, and more preferably 2 to 70 mole%. , More preferably 3 to 60 mole%. When the content of the constituent component derived from the monomer (a1) is in the above range, the resin cured film composed of the cured product of the photosensitive resin composition containing the polymer (III) will have better heat resistance.

In the polymer (III), the content of the constituent component of the unsaturated monomer (a4) derived from a functional group that reacts with an acid group is preferably 20 to 98 mol%, and more preferably 25 to 84 mol. %, More preferably 30 to 70 mole%. When the content of the constituents derived from the monomer (a4) is within the above range, in the step of producing the polymer (III), an appropriate amount of unsaturated group may be introduced into the branch of the precursor, and the polymer ( The resin cured film made of the cured product of the photosensitive resin composition III) will have better sensitivity.

In the polymer (III), the content of the constituents derived from other monomers (a3) is preferably 0 to 80 mole%, more preferably 5 to 70 mole%, and more preferably 10 to 60 mole%. ear%. By containing 80 mol% or less of the component derived from the monomer (a3), the pigment dispersibility of the polymer (III) can be appropriately improved, and the photosensitive resin composition containing the polymer (III) can be hardened. The properties of the resin-cured film made of materials such as heat resistance.

In the polymer (III), the content of the constituents derived from the unsaturated monobasic acid (a5) is preferably 20 to 98 mole%, more preferably 25 to 84 mole%, and more preferably 30 to 70 mole%. ear%. When the content of the constituent component derived from the unsaturated monobasic acid (a5) is in the above range, the sensitivity of the resin-cured film composed of the cured product of the photosensitive resin composition containing the polymer (III) will be better.

In the polymer (III), the content of the constituent component derived from the polybasic acid or the anhydride (a6) is preferably 16 to 78 mole%, more preferably 20 to 67 mole%, and more preferably 24 to 56. Mohr%. When the content of the component derived from the polybasic acid or the acid anhydride (a6) is within the above range, when the resin cured film composed of the cured product of the photosensitive resin composition containing the polymer (III) is subjected to alkaline development, the development is performed. The speed will be appropriate and better developability will be obtained.

(Production method of polymer (III))
As a method of manufacturing a polymer (III), the method shown below is mentioned, for example. First, a monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, an unsaturated monomer (a4) having a functional group that reacts with an acid group, and other monomers (a3) used as required ) To produce a precursor made of a copolymer by a method of copolymerization in accordance with a conventionally known radical polymerization method.
By the same method as the method for producing the polymer (I), and using an unsaturated monomer (a4) having a functional group that reacts with an acid group, the unsaturated acid monomer used in the production of the polymer (I) is replaced Body (a2), and can be made into a polymer (III) precursor.

Thereafter, the precursor, the unsaturated monoacid (a5) and the polybasic acid or the anhydride (a6) are reacted, and an acid group and a polymerizable unsaturated bond are introduced into the branch of the precursor to form a denatured polymer. This method can be used for manufacturing.
Specifically, for example, a precursor copolymer, an unsaturated monoacid (a5), a polybasic acid or the anhydride (a6), a polymerization inhibitor, and a catalyst are added to the reaction solvent at 50 to 150 ° C (preferably It is a method of subjecting it to a denaturation reaction at 80 to 130 ° C., whereby a polymer (III) can be produced.

When the monomer (a4) as a raw material of the polymer (III) is a precursor in which a radically polymerizable monomer having an epoxy group is used, and a copolymer having an unsaturated monomer having an epoxy group is produced as a precursor The following denaturation reactions occur.
When a precursor is reacted with an unsaturated monobasic acid (a5), the epoxy group existing in the precursor molecule is cleaved, and an unsaturated bond is introduced into a branch of the precursor, and a hydroxyl group is generated at the same time. The generated hydroxyl group reacts with the polybasic acid or the anhydride (a6), and the acid group is introduced into the branch of the precursor.

In addition, if any one or more of the monomers (a1), (a3), and (a4) as raw materials of the polymer (III) is a copolymer having a hydroxyl group and an unsaturated monomer having a hydroxyl group is used as the copolymer In the case of precursors, the following denaturation reactions occur.
When a precursor, an unsaturated monoacid (a5), and a polybasic acid or the anhydride (a6) are reacted, a hydroxyl group, an unsaturated monobasic acid (a5), and a polybasic acid or the anhydride (a6) present in the precursor molecule Reaction, unsaturated bonds and acid groups will be introduced into the precursor's branch chain.

In this embodiment, as the polymer (A), the polymer represented by the above (I), (II), or (III) has been described as an example, but the polymer (A) in the present invention may be The polymer may be a polymer having an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and is not limited to the polymer represented by the above (I), (II), or (III).

The method for producing the polymer (A) is not limited to the method for producing the polymer (I) (II) (III), and for example, the production method represented by the following (1) or (2) may be used.

(1) A method of copolymerizing the above-mentioned monomer (a1) and an unsaturated monomer containing an epoxy group to produce a precursor made of a copolymer. After that, the precursor is reacted with a polybasic acid anhydride to crack the epoxy group existing in the precursor molecule, and an acid group is introduced into the branch of the precursor to generate a hydroxyl group. Thereafter, the branched chain has an unsaturated bond including a hydroxyl group generated in the acid group precursor, and 2- (meth) acryloxyethyl isocyanate, 2- (meth) acrylmethyl ethyl isocyanate, and the like. The isocyanate compound reacts to introduce an unsaturated bond into the branch of the precursor.

(2) A method of copolymerizing the above-mentioned monomer (a1) and an unsaturated monomer containing a hydroxyl group to produce a precursor made of a copolymer. After that, the hydroxyl groups present in the precursor molecule are reacted with the polybasic acid anhydride and the isocyanate compound containing an unsaturated bond, respectively, and the acid group and the unsaturated bond are introduced into a branch of the precursor.

(Compound (B))
Compound (B), which contains a hydroxyl group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms. It is preferable that the compound (B) does not include an ethylenically unsaturated double bond in the structure. Since the resin composition of the present embodiment contains the compound (B), it has excellent storage stability.

As the acid group contained in the compound (B), for example, the same acid group as that of the polymer (A) can be used. Specifically, examples of the acid group contained in the compound (B) include a carboxyl group (-COOH), a sulfonic acid group (-SO ₃ H), and a phosphate group (-PO (OH) ₂ ). carboxyl. The compound (B) may have only one kind of acid group or two or more kinds of acid groups. The number of acid groups in the polymer (B) may be only one, or may be two or more.

As the bridged cyclic hydrocarbon group having 10 to 20 carbon atoms in the compound (B), the same as the bridged cyclic hydrocarbon group having 10 to 20 carbon atoms which the polymer (A) has can be used.
In the resin composition of this embodiment, the bridged cyclic hydrocarbon group having 10 to 20 carbon atoms included in the compound (B) and the bridged cyclic hydrocarbon group having 10 to 20 carbon atoms included in the polymer (A) may be It is the same or different, and the same is preferable. When the compound (B) and the polymer (A) are the same as the bridged cyclic hydrocarbon group resin composition having 10 to 20 carbon atoms, in the polymerization system for the polymerization reaction for producing the polymer (A), It is preferable to set not only the polymer (A) but also the compound (B). Specifically, the following method can be used: a method of selecting a raw material containing the compound (B) as a raw material of the polymer (A), and / or generating a compound (by a polymerization reaction for producing the polymer (A)) B). In this case, the polymerization system used for the polymerization reaction for producing the polymer (A) can be directly used as the resin composition of the present embodiment including the polymer (A) and the compound (B).

The bridged cyclic hydrocarbon group having 10 to 20 carbon atoms contained in the compound (B) is a group equivalent to a residue obtained by removing one hydrogen atom from the bridged cyclic hydrocarbon having 10 to 20 carbon atoms. In the same manner as the bridged cyclic hydrocarbon group of the polymer (A), among the bridged cyclic hydrocarbon groups having 10 to 20 carbon atoms of the compound (B), the skeleton of the bridged cyclic hydrocarbon is preferably the above-mentioned formula (3) The structure shown in (4) is more preferably a structure shown in (6) below.

(In the formula (6), R ¹¹ to R ¹³ each independently represent a hydrogen atom or a methyl group, and R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a methyl group, or a saturated or unsaturated ring formed by being connected to each other, * (It represents a bonding bond contained in the compound (B)).

In the structure represented by formula (6), R ¹¹ to R ^{15 are} preferably hydrogen atoms, and R ¹⁴ and R ^{15 are} preferably connected to each other to form a saturated or unsaturated 5-membered ring or 6-membered ring.

Specific examples of the compound (B) include one or more alcohols selected from the following alcohols and the reaction products of these alcohols and polybasic anhydride. The alcohol is selected from dicyclopentenol. (dicyclopentenyl alcohol), dicyclopentanyl alcohol, isobornyl alcohol, and Adamantyl alcohol. As a compound (B), these compounds can be used individually or in combination of 2 or more types.
As the compound (B), among the above-mentioned compounds, in terms of storage stability and the like, it is particularly preferable to use dicyclopentanol represented by the following formula (7) and / or represented by the following formula (8) The reaction product of dicyclopentanol and polybasic acid anhydride.

(In formula (8), R is a divalent linking group).

The compound (B) in the resin composition may be a compound that is intentionally added to the resin composition, or may be a polymerization system in which a part or all of the polymerization reaction is used to produce the polymer (A). Carry-in compounds. That is, the compound (B) may be a polymer (A) produced from a monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms as a raw material of the polymer (A), and the like. Compounds carried in the polymerization system of the polymerization reaction performed, and / or compounds produced during the production of the polymer (A).

The content of the compound (B) in the resin composition can be appropriately selected according to the purpose of use of the resin composition. The content of the compound (B) is 100 parts by mass based on the total of the polymer (A) and the compound (B). The amount is 0.001 to 1.0 parts by mass, preferably 0.005 to 0.7 parts by mass, and still more preferably 0.01 to 0.5 parts by mass.
When the content of the compound (B) is 0.001 parts by mass or more, the storage stability of the resin composition will be good. When the content of the compound (B) is 1.0 part by mass or less, it will be a resin composition containing the polymer (A) sufficiently. Therefore, a resin cured film (which is a cured product of a photosensitive resin composition containing a resin composition) has excellent heat resistance and developability.

(Solvent (C))
The resin composition according to this embodiment is a composition containing the polymer (A) and the compound (B), and may further include a solvent (C) if necessary.
The solvent (C) may be any inert solvent that does not react with the polymer (A). For example, the above-mentioned solvent (polymerization solvent) used in the production of the polymer (A) can be used, and propylene glycol is particularly preferred. (Poly) alkylene glycol monoalkyl ethers such as methyl ether, and (Poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate.

(Reactive diluent (D))
The resin composition of this embodiment may contain a reactive diluent (D) as needed. By including the reactive diluent (D), the viscosity of the resin composition can be adjusted and the processability can be improved, or the strength of the cured product of the resin composition and / or the adhesion to the substrate can be improved.

The compound used as the reactive diluent (D) is a polymerizable ethylenically unsaturated group having at least one polymerizable functional group in the molecule, and it is particularly preferable to use a compound having a plurality of polymerizable functional groups. . However, the reactive diluent (D) is set so as not to include the compound (B). Specifically, as a reactive diluent (D), the monofunctional monomer and / or polyfunctional monomer shown below can be used.

Examples of the monofunctional monomer include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (methyl) Acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, ( Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Ester, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloxy-2-hydroxypropyl phthalate, glycerol mono (methyl) Acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3, (meth) acrylate, (Meth) acrylic acid esters such as 3-tetrafluoropropyl ester, semi- (meth) acrylic acid ester of phthalic acid derivatives; styrene, α-methylstyrene, α-chloromethylstyrene, ethylene Aromatic vinyl compounds such as methyl toluene; carboxylic acid esters such as vinyl acetate, vinyl propionate, etc. . These monofunctional monomers can be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propylene glycol di (methyl). Acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) propenyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acrylic acid) Oxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, di Ethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, amine Base Ester (meth) acrylate (that is, toluene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, and the like with 2-hydroxyethyl (meth) acrylate, (Meth) acrylates such as triethyl (meth) acrylate of ethyl) isocyanurate; divinylbenzene, diallyl phthalate, diallyl phenylphosphonate, etc. Aromatic vinyl compounds; dicarboxylic acid esters such as divinyl adipate; triallyl tricyanate, methylenebis (meth) acrylamide, (meth) acrylamide Methylene ether, polycondensates of N-hydroxymethyl (meth) acrylamide and the like. These polyfunctional monomers can be used alone or in combination of two or more kinds.

As the reactive diluent (D), among the above monomers, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (methyl) are particularly preferred. Any of acrylates.

The resin composition according to this embodiment includes the polymer (A), the compound (B), and the solvent (C) described above. When a reactive diluent (D) is included as necessary, each component (the above (A) (B) The content of) (C) (D)) is appropriately selected depending on the purpose of use of the resin composition, and is preferably within the range shown below.
The content of the polymer (A) in the resin composition is preferably 100 to 100 parts by mass based on the total amount of the polymer (A), the compound (B), and the reactive diluent (D), and preferably 10 to 100 parts by mass. 20-80 parts by mass, more preferably 30-75 parts by mass.

The content of the solvent (C) in the resin composition is preferably 30 to 1,000 parts by mass based on 100 parts by mass of the total amount of the polymer (A), the compound (B), and the reactive diluent (D). It is more preferably 50 to 800 parts by mass, and even more preferably 100 to 700 parts by mass.

The content of the reactive diluent (D) in the resin composition is preferably from 0 to 90 parts by mass based on the total amount of the polymer (A), the compound (B), and the reactive diluent (D). It is preferably 20 to 80 parts by mass, and more preferably 25 to 70 parts by mass.
The total amount of the polymer (A), the compound (B), and the reactive diluent (D) in the resin composition is preferably 10 to 70% by mass, and more preferably 20 to 60% by mass.

When the content of the polymer (A), the compound (B), the solvent (C), and the reactive diluent (D) in the resin composition is within the above ranges, the resin will have a proper viscosity.组合 物。 Composition. Therefore, it is suitable as a material of the photosensitive resin composition mentioned later, and it can also be used suitably as a material of various coating agents, adhesives, and adhesives for printing inks.

(Production method of resin composition)
The resin composition of the present embodiment can use, for example, a known polymer (A), a compound (B), and a solvent (C) and a reactive diluent (D), which are used as required, by using a known one. The mixing device is manufactured by mixing.
When manufacturing the resin composition of this embodiment, as a polymer (A), the polymer (A) obtained by the polymerization system used for the polymerization reaction which manufactures a polymer (A) can be used.

Moreover, when manufacturing the resin composition of this embodiment, the polymer (A) contained in the polymerization system used for the polymerization reaction which manufactures a polymer (A), and the polymer (A) may be manufactured. The solvent used is directly used as a raw material of a resin composition. In this case, as for the solvent (C) used as a raw material of the resin composition, in addition to the solvent used in the production of the polymer (A), a desired solvent may be further added as necessary. The solvent (C) as a raw material of the resin composition may include a solvent other than the solvent (C) added together with the raw material of the resin composition.
In addition, if the polymerization system used for the polymerization reaction for producing the polymer (A) contains not only the polymer (A) but also the compound (B), the polymer (A) may be used to produce the polymer (A). The polymerization system of the polymerization reaction performed is used as it is as the resin composition of this embodiment containing a polymer (A) and a compound (B) as it is.

The resin composition according to this embodiment contains a polymer (A) having an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and a bridged ring containing a hydroxyl group or an acid group and 10 to 20 carbon atoms in a specific ratio. Compound (B) of the formula hydrocarbyl. Therefore, the resin composition of this embodiment is suitable as a material of a photosensitive resin composition, it can obtain the resin hardened film which has the outstanding developability, and has the outstanding storage stability.
In addition, since the resin composition of this embodiment has excellent storage stability, it is suitable as a material for various coating agents, adhesives, and adhesives for printing inks.

[2. Photosensitive resin composition]
The photosensitive resin composition of this embodiment contains the resin composition of this embodiment, a photopolymerization initiator (E), and a coloring agent (F) contained as needed. The photosensitive resin composition of this embodiment is polymerized and hardened by irradiation with light to form a cured product.

(Photopolymerization initiator (E))
The photopolymerization initiator (E) is not particularly limited, and examples thereof include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzidine oxime)], and ethyl Ketones, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (o-acetamoxime) and other oxime esters; benzene Acetoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, etc .; acetophenone, 2,2-dimethoxy-2-phenylacetophenone , 1,1-dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinyl-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone-1, and other acetophenones ; Anthraquinones such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; xanthone, thioxanthone, 2,4-dimethyl Thioxanthones such as thioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal ; Benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ', 4,4'-di (t-butyldioxy Carbonyl) benzophenones such as benzophenone; fluorenyl phosphine oxides and the like. These photopolymerization initiators (E) can be used alone or in combination of two or more kinds.

As the photopolymerization initiator (E), among the above-mentioned compounds, particularly the sensitivity of the i-line (365 nm) is high, and the yellowing of the cured product during curing and baking is less, and 2-formaldehyde is preferably used. Acetophenones such as 1,1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1,2-octanedione, 1- [4- (phenylthio)- , 2- (o-Benzamoxime)], ethyl ketone, 1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl]-, 1- (o-acetamoxime) and other oxime esters. These photopolymerization initiators can be used alone or in combination of two or more kinds, for example, depending on the intended sensitivity.

(Colorant (F))
As the colorant (F), those that can be dissolved or dispersed in the solvent (C) can be used, and examples thereof include dyes and / or pigments. For example, the colorant (F) may be a dye or a pigment alone, or a combination of a dye and a pigment, depending on the color of a pixel as an object produced by using the photosensitive resin composition. When a photosensitive resin composition is used as a material for a color filter, it is preferable to use a dye as the colorant (F) for the reasons described below. Pigments are particles and dyes are molecules. Therefore, when a dye is used as the colorant (F), as compared with a case where a pigment is used, the scattering of light in a color filter can be suppressed, and the brightness of an image display device including the color filter can be increased.

The dye is preferably used from the viewpoints of the solubility of the solvent (C) and the alkali developer, interaction with other components in the photosensitive resin composition, and heat resistance of the photosensitive resin composition. : Acid dyes having acidic groups such as carboxylic acids or sulfonic acids; salts of nitrogen compounds of acid dyes; sulfonamides of acid dyes; and the like. In particular, as the dye, anthraquinone-based, azo-based, xanthene-based, anthraquinone-based, or phthalocyanine-based dyes are preferably used. Among these, a photosensitive resin composition capable of obtaining a resin cured film with high transmittance is particularly preferably one or both of anthraquinone-based dyes and xanthene-based dyes.

Specifically, examples of the dye include acid alizarin violet N; acid black1, 2, 24, 48; acid blue1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69 , 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215 , 216, 217, 249, 252, 257, 260, 266, 274, 289, rhodamine B; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23 , 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow3, VALIFAST BLUE1603, 1605, 1621, 2606, 2620, 2670 and the And other derivatives. These dyes can be used alone or in combination of two or more kinds depending on the color of the target pixel, for example.

Examples of the pigment include: CIPigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 , 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CIPigment orange13, 31, 36, 38, 40, 42, 43, 51, 55, 59 , 61, 64, 65, 71, 73 and other orange pigments; CIPigment red9, 97, 105, 122, 123, 144, 149, 154, 166, 168, 176, 177, 180, 192, 209, 215, 216 , 224, 242, 254, 255, 264, 265 and other red pigments; CIPigment blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CIPigment violet 1, 19, 23, 29 , 32, 36, 38 and other purple pigments; CIPigment green 7, 36, 58, 59, 62 and other green pigments; CIPigment brown 23 and 25 and other brown pigments; CIPigment black 1, 7, carbon black, titanium black, Black pigments such as iron oxide. These pigments can be used alone or in combination of two or more kinds depending on the color of the intended pixel, for example.

When a pigment is used as the colorant (F), a known dispersant may be contained in the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment.
As the dispersant, a polymer dispersant having excellent dispersion stability over time is preferably used. Examples of the polymer dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene glycol diester-based dispersant, and dehydrated sorbitan. Alcohol aliphatic ester-based dispersants, aliphatic denatured ester-based dispersants, and the like. As the polymer dispersant, EFKA (manufactured by EFKA Chemicals (EFKA)), Disperbyk (manufactured by BYK), DISPARLON (manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (manufactured by Zeneca), etc. By.
The content of the dispersant in the photosensitive resin composition can be appropriately set depending on the type of pigment and the like to be used.

If the photosensitive resin composition of this embodiment contains the above-mentioned polymer (A), compound (B), solvent (C), reactive diluent (D), photopolymerization initiator (E), and responding agent When the coloring agent (F) is included as needed, each component can be appropriately selected according to the purpose of use of the photosensitive resin composition (the above (A), (B), (C), (D), (E), (F))). The content is preferably within the range shown below.

The content of the polymer (A) in the photosensitive resin composition is preferably 10 to 100 parts by mass based on the total amount of the polymer (A), the compound (B), and the reactive diluent (D). 90 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 30 to 75 parts by mass.

The content of the compound (B) in the photosensitive resin composition is preferably 0.001 to 1.0 parts by mass, and more preferably 0.005 based on 100 parts by mass of the total amount of the polymer (A) and the compound (B). ~ 0.7 parts by mass, more preferably 0.01 to 0.5 parts by mass.
The content of the solvent (C) in the photosensitive resin composition is preferably 30 to 1,000 parts by mass based on 100 parts by mass of the total amount of the polymer (A), the compound (B), and the reactive diluent (D). It is preferably 50 to 800 parts by mass, and more preferably 100 to 700 parts by mass.

The content of the reactive diluent (D) in the photosensitive resin composition is preferably 100 parts by mass based on the total amount of the polymer (A), the compound (B), and the reactive diluent (D). 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 25 to 70 parts by mass.

The content of the photopolymerization initiator (E) in the photosensitive resin composition is preferably 100 parts by mass based on the total amount of the polymer (A), the compound (B), and the reactive diluent (D). It is 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass.
The content of the coloring agent (F) in the photosensitive resin composition is preferably 5 to 100 parts by mass based on the total amount of the polymer (A), the compound (B), and the reactive diluent (D). 80 parts by mass, more preferably 5 to 70 parts by mass, and even more preferably 10 to 60 parts by mass.

If the above-mentioned polymer (A), compound (B), solvent (C), reactive diluent (D), photopolymerization initiator (E), and coloring agent (F) are contained in the photosensitive resin composition, When the amounts are within the above ranges, a curable resin composition having a suitable photocurability will be obtained.
Even if the photosensitive resin composition does not include the colorant (F), the above-mentioned polymer (A), compound (B), solvent (C), and reactive diluent in the photosensitive resin composition can be used. The contents of (D) and the photopolymerization initiator (E) are set within the above-mentioned ranges, respectively.

The photosensitive resin composition of this embodiment may contain well-known additives, such as a coupling agent, a leveling agent, and a thermal polymerization inhibitor, in order to provide predetermined characteristics in addition to the above-mentioned components. The content of the additives contained in the photosensitive resin composition is not particularly limited as long as the effect of the present invention is not impaired.

(Manufacturing method of photosensitive resin composition)
The photosensitive resin composition of this embodiment can use, for example, a resin composition of this embodiment, a photopolymerization initiator (E), and a coloring agent (F) contained as required, by using a known mixing device. To mix and produce.
In the manufacturing method of this embodiment, the above-mentioned polymer (A), compound (B), solvent (C), reactive diluent (D), and photopolymerization initiator ( E) The order of the components of the colorant (F) is not particularly limited. For example, the resin composition containing the polymer (A), the compound (B), and the solvent (C) can be prepared, and then reactively diluted. An agent (D), a photopolymerization initiator (E), and a coloring agent (F) are mixed with the obtained resin composition, and it manufactures.

Since the photosensitive resin composition of this embodiment contains the resin composition of this embodiment, a resin hardened film having excellent developability can be obtained, and excellent storage stability can be obtained. Therefore, the photosensitive resin composition of this embodiment is suitable as a resist. In particular, the photosensitive resin composition of this embodiment is suitable for use in the manufacture of solid-state imaging elements, organic EL displays, and liquid crystal display devices that are assembled into CCD (Charged-coupled devices) or CMOS (Complementary metal-oxide-semiconductor). Resistors used for transparent films, protective films, insulating films, overcoats, photospacers, black matrices, black columnar spacers, color filters, etc.

[3. Resin hardened film]
The resin cured film of this embodiment is a cured product of the photosensitive resin composition of this embodiment. The resin cured film of this embodiment can be suitably used as a material of a color filter. Hereinafter, as an example of the resin hardened film of this embodiment, a color filter is obtained by using the resin hardened film of this embodiment as an example.

The color filter of this embodiment includes a substrate, red (R), green (G), and blue (B) pixels formed on the substrate, a black matrix formed at the boundary of the pixels, and a pixel and Protective film on black matrix. The color filter of this embodiment includes a pixel and a black matrix composed of a cured product of the photosensitive resin composition of this embodiment. In the color filter of this embodiment, a well-known structure may be adopted as a structure other than a pixel and a black matrix.

The color filter of this embodiment can be manufactured, for example, by a method of sequentially forming red (R), green (G), and blue (B) pixels and a black matrix on a substrate.
The substrate is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyimide substrate, a polyimide substrate, a polyimide substrate, an aluminum substrate, and printed wiring can be appropriately used. Substrate, array substrate, etc.

Each pixel and the black matrix can be formed using a photolithography method. Specifically, after the above-mentioned photosensitive resin composition is applied to a substrate to form a coating film, the coating film is exposed through a photomask of a predetermined pattern, and the exposed portion is photocured. Then, the unexposed portion is developed with an alkaline aqueous solution, and then a predetermined pattern can be formed by baking.

The coating method of the photosensitive resin composition is not particularly limited, and a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, and the like can be used.
After coating the photosensitive resin composition, the solvent (C) contained in the photosensitive resin composition can be made by heating means such as a circulating baking oven, an infrared heater, and a heating plate as required. Volatile. The heating conditions are not particularly limited, and can be appropriately set depending on the type of the photosensitive resin composition to be used. For example, the heating temperature can be set to 50 ° C to 120 ° C, and the heating time can be set to 30 seconds to 30 minutes.

As a method for exposing a coating film composed of a photosensitive resin composition, specifically, the following method can be mentioned: the coating film is irradiated with ultraviolet rays, excimer laser light, etc. through a negative mask. Active energy ray to make partial exposure. The amount of active energy rays irradiated by the coating film may be appropriately selected according to the composition of the photosensitive resin composition, and is preferably 30 to 2000 mJ / cm ² , for example. The light source used in the exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used.

The alkaline aqueous solution used in the development of the exposed coating film is not particularly limited, and it can be used: aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc .; ethylamine, diethyl Aqueous solution of amine compounds such as amines and dimethylethanolamine; tetramethylammonium, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N- Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N -Ethyl-N-β-methoxyethylaniline and an aqueous solution of a p-phenylenediamine-based compound such as sulfate, hydrochloride or p-toluenesulfonate. To such an alkaline aqueous solution, an antifoaming agent or a surfactant may be added as required.

In the present embodiment, after the exposed coating film is developed using the above-mentioned alkali aqueous solution, it is preferably washed with water and dried.
The conditions for baking the developed coating film are not particularly limited, as long as the heat treatment is performed in accordance with the type of the photosensitive resin composition used. For example, the baking temperature may be 250 ° C or lower, preferably 240 ° C or lower, and particularly preferably 230 ° C or lower. For example, the baking time can be set to 10 minutes to 4 hours, and preferably 20 minutes to 2 hours.

In this manner, the steps of coating, exposing, developing, and baking are sequentially repeated for the photosensitive resin composition corresponding to each pixel and the black matrix. Thereby, each pixel and a black matrix which have a desired shape which consists of the hardened | cured material of the photosensitive resin composition of this embodiment can be formed.

Since the resin hardened film of this embodiment is a hardened | cured material of the photosensitive resin composition of this embodiment which has the outstanding storage stability, it can manufacture stably.
In this embodiment, each pixel and a black matrix composed of a cured product of the photosensitive resin composition of this embodiment will be described as examples, but the cured product of this embodiment is not limited to the above examples. For example, a hardened product composed of a photosensitive resin composition not containing a colorant (F) is suitable as a protective layer, a protective film, an insulating film, etc. incorporated in a solid-state imaging element, an organic EL display, or a liquid crystal display device. use.

The embodiment described above is a description of the photosensitive resin composition including the resin composition and the photopolymerization initiator (E) of this embodiment, but may include a hardening accelerator and a known epoxy resin instead of photopolymerization. The initiator (E) is used to shape the curable resin composition. This curable resin composition can be formed into a desired pattern by, for example, applying it to a substrate by an inkjet method, and then heating it.

[4. Image display element]
The image display element of this embodiment includes the resin cured film of this embodiment. As an image display element of this embodiment, the image display element which has the color filter obtained using the resin hardened film of this embodiment is mentioned, for example.
Specific examples of the image display element of this embodiment include solid-state imaging elements such as CCDs and CMOS, organic EL displays, and liquid crystal display devices.

As an image display element of this embodiment, for example, when a liquid crystal display element is manufactured, a color filter obtained by using the resin cured film of this embodiment is formed on a first substrate. Next, electrodes and spaces are sequentially formed. Pieces, etc. Then, an electrode or the like is formed on the second substrate, and the color filter forming surface of the first substrate and the electrode forming surface of the second substrate are bonded to face each other, and the first substrate and the second substrate are bonded together. The specified amount of liquid crystal is injected and sealed.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited to the following examples.

`` Resin composition ''
Examples 1 to 1 of the compound (B) containing a polymer (A), a hydroxyl group or an acid group, and a bridged cyclic hydrocarbon group having 10 to 20 carbons in the proportions shown in Table 1 were produced by the methods shown below. 9. The resin compositions of Comparative Examples 1 to 4 were evaluated.

(Example 1)
"Synthesis of Polymer (III)"
In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 175.0 g of propylene glycol monomethyl ether acetate was added as a solvent, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 ° C. Next, 66.0 g of dicyclopentyl methacrylate, which is a monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and unsaturated monomer (a4), which is a functional group that reacts with an acid group. A monomer mixture consisting of 85.2 g of glycidyl methacrylate and 10.4 g of styrene as another monomer (a3) was added with 17.8 g of t-butylperoxy-2-ethylhexanoate (polymerized The initiator, Perbutyl O), manufactured by Nippon Oil Co., was dropped into the flask from the dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to perform a copolymerization reaction to obtain a first polymer (precursor).

Next, the flask was replaced with 6% oxygen, and 43.2 g of acrylic acid as an unsaturated monoacid (a5), 0.6 g of triphenylphosphine as a catalyst, and hydroquinone as a polymerization inhibitor were added to the flask. 0.1 g was added at 120 ° C for 6 hours to form a second polymer.

Next, 59.3 g of tetrahydrophthalic anhydride as a polybasic acid or the anhydride (a6) was added to the second polymer, and an addition reaction was performed at 115 ° C for 3 hours to produce a polymer as the polymer (A). (III).
About the obtained polymer (A), the acid value and weight average molecular weight were measured by the method shown below. As a result, the solid content of the polymer (A) had an acid value of 80 mgKOH / g and a weight average molecular weight of 8,000.

"Acid value"
The acid value of the polymer (A) measured in accordance with JIS K6901: 2008 5.3.2. Specifically, it means the meaning of the mg number of potassium hydroxide required when neutralizing the acidic component contained in 1g of polymers (A).

"Weight average molecular weight (Mw)"
The weight average molecular weight (Mw) means a standard polystyrene conversion measured by the following conditions using gel permeation chromatography (GPC) (Shodex (registered trademark) GPC-101 (manufactured by Showa Denko Corporation)). Meaning of weight average molecular weight.
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Corporation)
Column temperature: 40 ℃
Sample: 0.2% by mass tetrahydrofuran solution of copolymer. Development solvent: tetrahydrofuran detector: differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko Corporation)
Flow rate: 1mL / min

Next, 281.9 g of the polymer (A), 0.1 g of dicyclopentanol as the compound (B) containing a hydroxyl group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and propylene glycol monomer as the solvent (C) 169.5 g of methyl ether was mixed to obtain the resin composition of Example 1 (the concentration of the component after removing the solvent (C) was 45% by mass). The content of the compound (B) contained in the resin composition of Example 1 was calculated by the method shown below. As a result, the content of the compound (B) was 0.05 parts by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

The resin composition of Example 1 is a polymer (A) included in the polymerization system to be used for the polymerization reaction for producing the polymer (A), and a solvent used in producing the polymer (A). , Directly used as raw materials together. As the compound (B), a compound carried in a polymerization system for a polymerization reaction for producing the polymer (A), and a compound intentionally added as a raw material of a resin composition are used.

"Content of Compound (B)"
The content of the compound (B) means the meaning of the content of the compound (B) measured under the following conditions using gas chromatography (GC-2010 (manufactured by Shimadzu Corporation)).
Column: ZB-5 (manufactured by phenomenex)
Column temperature: 50 ℃ → 20 ℃ / min → 250 ℃
Sample: 0.2 mass% acetone solution of resin composition Carrier gas: Helium detector: Hydrogen flame ionization detector (FID-2010)
Pressure: 120kPa

(Example 2)
The resin composition of Example 2 was obtained in the same manner as in Example 1 except that the amount of the compound (B) added intentionally as a raw material of the resin composition was changed to 0.5 g. The content of the compound (B) contained in the resin composition of Example 2 was 0.2 parts by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

(Example 3)
The resin composition of Example 3 was obtained in the same manner as in Example 1 except that the amount of the compound (B) added intentionally as a raw material of the resin composition was changed to 1.0 g. The content of the compound (B) contained in the resin composition of Example 3 was 0.4 parts by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

(Example 4)
"Synthesis of Polymer (I)"
In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 101.2 g of propylene glycol monomethyl ether acetate was added as a solvent, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 ° C. Next, 22.0 g of dicyclopentyl methacrylate as the monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, 24.1 g of methacrylic acid as the unsaturated acid monomer (a2), and As a monomer mixture composed of 109.1 g of benzyl methacrylate as another monomer (a3), 3.1 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Corporation) was added. Perbutyl O), and it was dripped into the said flask from the dropping funnel for 2 hours. After completion of the dropwise addition, the polymer (I) was obtained as a polymer (A) by performing a copolymerization reaction by stirring at 120 ° C for 2 hours.

About the obtained polymer (A), it carried out similarly to Example 1, and measured the acid value and weight average molecular weight. As a result, the acid value of the solid content of the polymer (A) was 105 mgKOH / g, and the weight average molecular weight was 17,000.

Next, 158.3 g of the polymer (A), 0.1 g of dicyclopentanol as the compound (B) containing a hydroxyl group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and propylene glycol monomer as the solvent (C) 92.3 g of methyl ether was mixed to obtain the resin composition of Example 4 (the concentration of the component after removing the solvent (C) was 45%).
The content of the compound (B) contained in the resin composition of Example 4 was measured in the same manner as in Example 1. As a result, the content of the compound (B) was 0.1 part by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

(Example 5)
A resin composition of Example 5 was obtained in the same manner as in Example 4 except that the amount of the compound (B) added intentionally as a raw material of the resin composition was changed to 0.2 g. The content of the compound (B) contained in the resin composition of Example 5 was 0.2 parts by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

(Example 6)
The resin composition of Example 6 was obtained in the same manner as in Example 4 except that the amount of the compound (B) added intentionally as a raw material of the resin composition was changed to 0.5 g. The content of the compound (B) contained in the resin composition of Example 6 was 0.4 parts by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

(Example 7)
"Synthesis of Polymer (II)"
In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 195.6 g of propylene glycol monomethyl ether acetate was added as a solvent, and the mixture was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Next, 22.0 g of dicyclopentyl methacrylate as the monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, 49.9 g of methacrylic acid as the unsaturated acid monomer (a2), and As a monomer mixture composed of 56.3 g of benzyl methacrylate as another monomer (a3), 2.2 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Corporation) was added. Perbutyl O), and it was dripped into the said flask from the dropping funnel for 2 hours. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 2 hours to perform a copolymerization reaction to obtain a first polymer (polymer (I)).

Next, the flask was replaced with 6% oxygen, and 43.3 g of glycidyl methacrylate as an unsaturated monomer (a4) having a functional group reactive with an acid group was added to the flask. 0.5 g of triphenylphosphine and 0.1 g of hydroquinone as a polymerization inhibitor were subjected to an addition reaction at 120 ° C. for 6 hours to produce a polymer (II) as a polymer (A).

About the obtained polymer (A), it carried out similarly to Example 1, and measured the acid value and weight average molecular weight. As a result, the acid value of the solid content of the polymer (A) was 90 mgKOH / g, and the weight average molecular weight was 30,000.

Next, 173.7 g of polymer (A), 0.4 g of dicyclopentanol as a compound (B) containing a hydroxyl group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and propylene glycol monoamine as a solvent (C) 16.7 g of methyl ethers were mixed, and the resin composition of Example 7 was obtained (the component concentration after removing the solvent (C) was 45% by mass).
The content of the compound (B) contained in the resin composition of Example 7 was calculated in the same manner as in Example 1. As a result, the content of the compound (B) was 0.3 parts by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

(Example 8)
The resin composition of Example 8 was obtained in the same manner as in Example 7 except that the amount of the compound (B) added intentionally as a raw material of the resin composition was changed to 0.1 g. The content of the compound (B) contained in the resin composition of Example 8 was 0.1 part by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

(Example 9)
A resin composition of Example 9 was obtained in the same manner as in Example 7 except that the amount of the compound (B) added intentionally as a raw material of the resin composition was changed to 0.7 g. The content of the compound (B) contained in the resin composition of Example 9 was 0.5 part by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

(Comparative example 1)
"Synthesis of Polymer (I)"
In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 99.0 g of propylene glycol monomethyl ether acetate was added as a solvent, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 ° C. Next, 0.2 g of dicyclopentyl methacrylate as the monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, 23.2 g of methacrylic acid as the unsaturated acid monomer (a2), and As a monomer mixture composed of 128.3 g of benzyl methacrylate as another monomer (a3), 3.0 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Corporation) was added. Perbutyl O), and it was dripped into the said flask from the dropping funnel for 2 hours. After completion of the dropwise addition, the polymer (I) was obtained as a polymer (A) by performing a copolymerization reaction by stirring at 120 ° C for 2 hours.

About the obtained polymer (A), it carried out similarly to Example 1, and measured the acid value and weight average molecular weight. As a result, the solid content of the polymer (A) had an acid value of 105 mgKOH / g and a weight average molecular weight of 16,800.

Next, the polymer (A) and 90.2 g of propylene glycol monomethyl ether as a solvent (C) were mixed to obtain a resin composition of Comparative Example 1 (the concentration of the component after removing the solvent (C) was 45%). .
The content of the compound (B) contained in the resin composition of Comparative Example 1 was calculated in the same manner as in Example 1. As a result, the content of the compound (B) was 0.0008 parts by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

(Comparative example 2)
"Synthesis of Polymer (II)"
In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 193.0 g of propylene glycol monomethyl ether acetate was added as a solvent, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 ° C. Next, 0.2 g of dicyclopentyl methacrylate as the monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, 47.3 g of methacrylic acid as the unsaturated acid monomer (a2), and As a monomer mixture composed of 79.0 g of benzyl methacrylate as another monomer (a3), 2.2 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Corporation) was added. Perbutyl O), and it was dripped into the said flask from the dropping funnel for 2 hours. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 2 hours to perform a copolymerization reaction to obtain a first polymer (polymer (I)).

Next, the flask was replaced with 6% oxygen, and 41.2 g of glycidyl methacrylate as an unsaturated monomer (a4) having a functional group reactive with an acid group was added to the flask. 0.5 g of triphenylphosphine and 0.1 g of hydroquinone as a polymerization inhibitor were subjected to an addition reaction at 120 ° C. for 6 hours to produce a polymer (II) as a polymer (A).

About the obtained polymer (A), it carried out similarly to Example 1, and measured the acid value and weight average molecular weight. As a result, the acid value of the solid content of the polymer (A) was 90 mgKOH / g, and the weight average molecular weight was 29,500.

Next, the polymer (A) and 14.6 g of propylene glycol monomethyl ether as a solvent (C) were mixed to obtain a resin composition of Comparative Example 2 (the concentration of the component after removing the solvent (C) was 45%). .
The content of the compound (B) contained in the resin composition of Comparative Example 2 was calculated in the same manner as in Example 1. As a result, the content of the compound (B) was 0.0008 parts by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

(Comparative example 3)
"Synthesis of Polymer (III)"
In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 135.4 g of propylene glycol monomethyl ether acetate was added as a solvent, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 ° C. Next, 0.9 g of dicyclopentyl methacrylate, which is a monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and unsaturated monomer (a4, which is a functional group that reacts with an acid group) A monomer mixture consisting of 76.7 g of glycidyl methacrylate and 47.4 g of styrene as another monomer (a3) was added with 13.8 g of t-butylperoxy-2-ethylhexanoate (polymerized The initiator, Perbutyl O), manufactured by Nippon Oil Co., was dropped into the flask from the dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to perform a copolymerization reaction to obtain a first polymer (precursor).

Next, the flask was replaced with 6% oxygen, and 38.9 g of acrylic acid as an unsaturated monoacid (a5), 0.5 g of triphenylphosphine as a catalyst, and hydroquinone as a polymerization inhibitor were added to the flask. 0.1 g was added at 120 ° C for 6 hours to form a second polymer.

Next, 53.2 g of tetrahydrophthalic anhydride as a polybasic acid or the anhydride (a6) was added to the second polymer, and an addition reaction was performed at 115 ° C for 3 hours to polymerize the polymer (A).物 (III).
About the obtained polymer (A), it carried out similarly to Example 1, and measured the acid value and weight average molecular weight. As a result, the acid value of the solid content of the polymer (A) was 80 mgKOH / g, and the weight average molecular weight was 7,700.

Next, the polymer (A) and 146.8 g of propylene glycol monomethyl ether as a solvent (C) were mixed to obtain a resin composition of Comparative Example 3 (the concentration of the component after removing the solvent (C) was 45%). .
The content of the compound (B) contained in the resin composition of Comparative Example 3 was calculated in the same manner as in Example 1. As a result, the content of the compound (B) was 0.0006 parts by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B).

(Comparative Example 4)
"Synthesis of Polymer (III)"
As the dicyclopentyl methacrylate having a bridged cyclic hydrocarbon group monomer (a1) having 10 to 20 carbon atoms, the same procedure as in Comparative Example 3 was performed except that a material different from the manufacturer was used, and the resultant was polymerized. (III) of polymer (A).
About the obtained polymer (A), it carried out similarly to Example 1, and measured the acid value and weight average molecular weight. As a result, the acid value of the solid content of the polymer (A) was 80 mgKOH / g, and the weight average molecular weight was 7,800.

Next, the polymer (A) and 146.8 g of propylene glycol monomethyl ether as a solvent (C) were mixed to obtain a resin composition of Comparative Example 4 (the concentration of the component after removing the solvent (C) was 45%). .
The content of the compound (B) contained in the resin composition of Comparative Example 4 was calculated in the same manner as in Example 1. As a result, the content of the compound (B) was below the detection limit (less than 0.0001 parts by mass with respect to 100 parts by mass of the total of the polymer (A) and the compound (B)).

＜ Evaluation of resin composition ＞
The resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were evaluated for storage stability by the methods shown below.
An equal amount (10 g) of the resin composition was weighed into a 20 ml glass container as a sample. These samples were placed in a thermostat maintained at 40 ° C. for one week, and stored. The state of the samples was evaluated according to the criteria shown below.
The weight average molecular weight (Mw) of the polymer (A) contained in the resin composition after storage is the same as the weight average molecular weight (Mw) of the polymer (A) used as a raw material of the resin composition. To measure. The results are shown in Table 1.

○: The amount of increase in the weight average molecular weight of the polymer (A) contained in the resin composition after storage is less than 3 as compared with the weight average molecular weight of the polymer (A) used as the raw material of the resin composition. %.
×: The increase in the weight average molecular weight of the polymer (A) contained in the resin composition after storage is 3% or more compared to the weight average molecular weight of the polymer (A) used as a raw material of the resin composition. .

As shown in Table 1, the storage stability evaluation of the resin compositions of Examples 1 to 9 was ○. In comparison, the storage stability of the resin compositions of Comparative Examples 1 to 4 was evaluated as ×.
This is assumed to be because the resin compositions of Examples 1 to 9 contain sufficient effects of the compound (B).

"Curable resin composition (color resist)"
The samples after the storage stability evaluation of the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were used to prepare a color photoresist (hardened) containing the components shown in Table 2 in the ratio shown in Table 2. Sexual resin composition).
The amount of the solvent (C) in Table 2 does not include the amount of the solvent (the solvent contained in the resin composition) used in the production of the polymer (A). The formulation amount of the resin composition in Table 2 includes the amount of the solvent (the solvent contained in the resin composition) used in the production of the polymer (A).

＜ Evaluation of color photoresistance ＞
For the color resists of Examples 1 to 9 and Comparative Examples 1 to 4, the developability was evaluated by the methods shown below.
A color photoresist was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness after exposure became 2.5 μm to form a coating film, and the solvent was evaporated by heating at 90 ° C. for 3 minutes. Next, a photomask of a specified pattern was placed at a distance of 100 μm from the coating film, and the coating film was exposed (exposure amount 150 mJ / cm ² ) through the photomask to harden the exposed portion.
Next, an aqueous solution containing 0.1% by mass of sodium carbonate was sprayed at a temperature of 23 ° C. and a pressure of 0.3 MPa to dissolve and develop the unexposed portion. Thereafter, it is baked at 210 ° C for 30 minutes, thereby forming a predetermined pattern.

Then, the pattern after alkali development was observed using an electron microscope S-3400 manufactured by Hitachi High Technologies to confirm the residue after alkali development, and the evaluation was performed on the basis shown below. The results are shown in Table 1.
(Circle): There is no residue of an unexposed part.
X: Residue with unexposed parts.

As shown in Table 1, the developability of the color resists of Examples 1 to 9 was evaluated as ○. In comparison, the developability of the color resists of Comparative Examples 1 to 4 was evaluated as ×.
This is assumed to be because the color photoresist of Examples 1 to 9 contains a sufficient effect of the compound (B).

[Industrial availability]

According to the present invention, it is possible to provide a resin composition suitable as a material of a photosensitive resin composition, which can obtain a resin cured film having excellent developability and has excellent storage stability.
The photosensitive resin composition of the present invention can obtain a resin hardened film having excellent developability and excellent storage stability. Therefore, the photosensitive resin composition of the present invention is preferably used as a resist for a transparent film, a protective film, an insulating film, a protective layer, a light spacer, a black matrix, a black columnar spacer, and a color filter.

Claims (13)

A resin composition comprising:
A polymer (A) having an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbons and a compound (B) containing a hydroxyl group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbons,
The compound (B) is selected from any one or more of the following alcohols and reaction products of the alcohols and polybasic acid anhydrides, and the aforementioned alcohols are selected from dicyclopentenol and dicyclopentanol,
The compound (B) is included in an amount of 0.001 to 1.0 part by mass based on 100 parts by mass of the total of the polymer (A) and the compound (B). The resin composition according to claim 1, wherein the compound (B) further contains at least one selected from the group consisting of amantadine and a reaction product of the amantadine and a polybasic acid anhydride. The resin composition according to claim 1 or claim 2, wherein the polymer (A) has an unsaturated bond. The resin composition according to claim 1 or claim 2, further comprising a solvent (C). The resin composition according to claim 1 or claim 2, further comprising a reactive diluent (D). A photosensitive resin composition comprising the resin composition according to any one of claim 1 to claim 5 and a photopolymerization initiator (E). The photosensitive resin composition according to claim 6, wherein the photopolymerization initiator (E) is one or both of the acetophenone-based and the oxime ester-based. The photosensitive resin composition according to claim 6 or claim 7, further comprising a colorant (F). The photosensitive resin composition according to claim 8, wherein the colorant (F) contains a dye. The photosensitive resin composition according to claim 9, wherein the colorant (F) is one or both of an anthraquinone dye and a xanthene dye. A resin cured film, which is a cured product of the photosensitive resin composition according to any one of claim 6 to claim 10. An image display element comprising a resin cured film as claimed in claim 11. A color filter comprising a cured product of a photosensitive resin composition according to any one of claim 6 to claim 10.