JP2019112494A - Resin composition, photosensitive resin composition, resin cured film, image display element and color filter - Google Patents

Abstract

To provide a resin composition which obtains a resin cured film having excellent developability, and is suitable as a material of a photosensitive resin composition having excellent storage stability.SOLUTION: A resin composition contains a polymer (A) having an acid group and a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms and a compound (B) having a hydroxy group or an acid group and a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms, and contains 0.001-1.0 pts.mass of the compound (B) with respect to 100 pts.mass of the total of the polymer (A) and the compound (B). The compound (B) is preferably one or more selected from alcohol selected from dicyclopentenyl alcohol, dicyclopentanyl alcohol, isobornyl alcohol and adamanthyl alcohol, and a reaction product of the alcohol and a polybasic acid anhydride.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a photosensitive resin composition, a cured resin film, and an image display device including the same.

  In recent years, from the viewpoint of resource saving and energy saving, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams are widely used in the fields of various coatings, printing, paints, adhesives and the like. Photosensitive resin compositions are used as solder resists, resists for color filters, and the like in the field of electronic materials such as printed wiring boards.

  The 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 a black matrix formed at the boundary of the pixels. And a protective film formed on the pixel and the black matrix. The color filter is usually manufactured by sequentially forming a black matrix, each pixel and a protective film on a transparent substrate.

  Various manufacturing methods have been proposed as methods for forming each pixel and the black matrix. At present, a method using a photosensitive resin composition as a resist and using a photolithography method which repeats coating, exposure, development and baking has become mainstream as a method of forming each pixel and black matrix. Each pixel and black matrix formed using this method are excellent in light resistance and heat resistance, and have few defects such as pinholes.

  Generally, the photosensitive resin composition used in the photolithography method contains a resin, a reactive diluent, a photopolymerization initiator, a colorant and a solvent. The photosensitive resin composition used for the photolithography method needs to have developability.

Conventionally, as resins used for photosensitive resin compositions, resins which are copolymers of unsaturated carboxylic acids and / or unsaturated carboxylic acid anhydrides, radically polymerizable compounds having an epoxy group, and other radically polymerizable compounds It is proposed (for example, refer patent document 1).
Moreover, it synthesize | combined using glycidyl (meth) acrylate as resin used for the photosensitive resin composition, the copolymer which does not have an acidic radical and whose weight average molecular weights of polystyrene conversion are 1000-50000, and an acidic radical A resin composition is proposed that contains a copolymer having a weight average molecular weight of 1000 to 50000 in terms of polystyrene equivalent (see, for example, Patent Document 2).

Japanese Patent Application Publication No. 06-043643 JP, 2015-222279, A

However, conventional photosensitive resin compositions have insufficient storage stability.
The present invention has been made in view of the above circumstances, and a resin composition suitable as a material of a photosensitive resin composition which can obtain a cured resin film having excellent developability and which has excellent storage stability is provided. The task is to provide.
Another object of the present invention is to provide a photosensitive resin composition which contains the resin composition of the present invention, provides a cured resin film having excellent developability, and has excellent storage stability.
Moreover, this invention makes it a subject to provide the resin cured film which is a hardened | cured material of the photosensitive resin composition of this invention, and an image display element which comprises this.

The present inventor has intensively studied to solve the above-mentioned problems.
As a result, it contains a polymer (A) having an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and a hydroxy group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms The present invention was conceived based on the finding that a resin composition containing the compound (B) in a specific ratio may be used.
That is, the present invention relates to the following matters.

[1] A polymer (A) having an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and a hydroxy group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms The compound (B) is contained, and 0.001 to 1.0 parts by mass of the compound (B) is contained with respect to a total of 100 parts by mass of the polymer (A) and the compound (B). Resin composition.
[2] The compound (B) is selected from the reaction product of an alcohol selected from dicyclopentenyl alcohol, dicyclopentanyl alcohol, isobornyl alcohol, adamantyl alcohol, and the alcohol and a polybasic acid anhydride The resin composition as described in [1] which is any 1 type or more.

[3] The resin composition as described in [1] or [2], wherein the polymer (A) has a unsaturated bond.
[4] The resin composition according to any one of [1] to [3], further containing a solvent (C).
[5] The resin composition according to any one of [1] to [4], further containing 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 type and an oxime ester type.
[8] The photosensitive resin composition according to [6] or [7], further containing a coloring agent (F).
[9] The photosensitive resin composition according to [8], wherein the coloring agent (F) contains a dye.
[10] The photosensitive resin composition according to [9], wherein the colorant (F) is one or both of an anthraquinone dye and a xanthene dye.

[11] A cured resin film characterized by being a cured product of the photosensitive resin composition according to any one of [7] to [10].
[12] An image display element comprising the cured resin film according to [11].

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

Hereinafter, the resin composition, the photosensitive resin composition, the cured resin film, and the image display element of the present invention will be described in detail. The present invention is not limited to only the embodiments shown below.
[1. Resin composition]
The resin composition of the present invention comprises a polymer (A) having an acid group and a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms, and a hydroxy group or an acid group and a crosslinked cyclic carbon having 10 to 20 carbon atoms And a compound (B) containing a hydrogen group.
Heretofore, it has not been known that the compound (B) has a function of improving the storage stability of the polymer (A). Therefore, in order to improve the storage stability of the polymer (A), the addition of the component (B) to the polymer (A) has not been conventionally performed.
MEANS TO SOLVE THE PROBLEM This inventor earnestly studies in order to solve the said subject, and is a resin containing 0.001-1.0 mass part of compounds (B) with respect to a total of 100 mass parts of a polymer (A) and a compound (B). By making it into a composition, it discovered that the resin cured film which has the outstanding developability was obtained, and the resin composition which has the outstanding storage stability was obtained, and considered the present invention.

(Polymer (A))
The polymer (A) is not particularly limited as long as it has an acid group and a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms in the molecule. It is preferable that a polymer (A) has a polymerization unit containing an acidic radical and a C10-C20 bridged cyclic hydrocarbon group.
Since the polymer (A) has an acid group in the molecule, a resin cured film made of a cured product of the photosensitive resin composition containing the polymer (A) has good alkali developability. Moreover, since a polymer (A) has a C10-C20 bridged cyclic hydrocarbon group in a molecule, the resin cured film which consists of hardened | cured material of the photosensitive resin composition containing a polymer (A) is heat resistance. Is good.

The acid groups included in the polymer (A), for example, a carboxy group (-COOH), a sulfo group _(-SO 3 H), a phosphoric acid group (-PO _{(OH) 2)} can be mentioned, with carboxyl groups Is particularly preferred. The developability of the resin cured film which consists of hardened | cured material of the photosensitive resin composition containing a polymer (A) as the acid group which a polymer (A) has is a carboxy group becomes more favorable. The polymer (A) may have only one type of acid group, or two or more types of acid groups. Moreover, the number of the acid groups which each polymerization unit of a polymer (A) has may be only one, and may be two or more.

  The crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms possessed by the polymer (A) is a group corresponding to the remaining part of the crosslinked cyclic hydrocarbon having 10 to 20 carbon atoms excluding one hydrogen atom. is there. The skeleton of the bridged cyclic hydrocarbon in the bridged cyclic hydrocarbon group possessed by the polymer (A) is preferably a structure represented by the following formula (3) and / or formula (4), specifically And adamantane skeleton, norbornane skeleton and the like. The crosslinked cyclic hydrocarbon group possessed by the polymer (A) is a group corresponding to the remaining part of the structure represented by the following formula (3) and / or formula (4) from which one hydrogen atom has been removed. Is preferred.

（式（３）中、Ａ^１、Ｂ^１は、それぞれ、直鎖または分岐アルキレン基（環式を含む。）を示し、Ｒ^４は水素原子またはメチル基を示す。Ａ^１、Ｂ^１は同一であっても、異なっていてもよく、Ａ^１、Ｂ^１の分枝同士がつながって環状となっていてもよい。）

(In Formula (3), A ¹ and B ¹ each represent a linear or branched alkylene group (including a cyclic group), R ⁴ represents a hydrogen atom or a methyl group, and A ¹ and B ¹ are the same. Even if it is, it may differ and the branches of A ¹ and B ¹ may be connected to form a ring.)

（式（４）中、Ａ^２、Ｂ^２、Ｌは、それぞれ、直鎖または分岐アルキレン基（環式を含む。）を示し、Ｒ^５は水素原子またはメチル基を示す。Ａ^２、Ｂ^２、Ｌは同一であっても、異なっていてもよく、Ａ^２、Ｂ^２、Ｌの分枝同士がつながって環状となっていてもよい。）

(In the formula ^{(4), A 2, B} 2, L , respectively, represents a straight-chain or branched-alkylene radical (including cyclic.), ^.A 2 ^{R 5} is showing a hydrogen atom or a methyl group, ^{B 2} And L may be the same or different, and the branches of A ² , B ² and L may be connected to form a ring.)

  The acid value (JIS K 6901 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 10 to 300 KOHmg / g, more preferably 20 to 200 KOHmg / g. is there.

  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 resin (A) has a weight-average molecular weight of 1,000 or more, when a resin-cured film made of a cured product of the photosensitive resin composition containing the polymer (A) is developed, chipping of the pattern hardly occurs. Better developability is obtained. When the weight average molecular weight of the polymer (A) is 50,000 or less, the developing time when developing a resin cured film made of a cured product of the photosensitive resin composition containing the polymer (A) does not become too long Is practical.

The "weight average molecular weight (Mw)" in the present specification means a standard polystyrene equivalent weight average molecular weight measured under the following conditions using gel permeation chromatography (GPC).
Column: Showdex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2% tetrahydrofuran solution of copolymer Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Showex (registered trademark) RI-71S) (manufactured by Showa Denko KK)
Flow rate: 1 mL / 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) has high sensitivity. The polymer (A) having an unsaturated bond is preferably the polymer (II) or the polymer (III) described later.
The unsaturated bond equivalent in the polymer (A) having unsaturated bonds is preferably 100 to 4,000 g / mol, and more preferably in the range of 300 to 2,000 g / mol.

The "unsaturated bond equivalent" in the present specification is the mass of the polymer per 1 mol of unsaturated bond of the polymer (polymer). The unsaturated bond equivalent is determined by dividing the mass of the polymer by the number of moles of unsaturated bonds of the polymer contained therein (g / mol).
In the present specification, as the unsaturated bond equivalent, a theoretical value calculated from the raw materials used for producing the polymer and the raw materials used for introducing the unsaturated bond is used.

  The heat resistance and developability of the resin cured film which consists of hardened | cured material of the photosensitive resin composition containing polymer (A) as the unsaturated bond equivalent in polymer (A) which has unsaturated bond is 100 g / mol or more are more Improve further. A resin cured film made of a cured product of a photosensitive resin composition containing a polymer (A) has a higher sensitivity when the unsaturated bond equivalent of the polymer (A) having an unsaturated bond is 4,000 g / mol or less It becomes.

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

Polymer (I); Component derived from a monomer (a1) having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms, component derived from an unsaturated acid monomer (a2), and other monomers optionally used (A3) A copolymer having a polymerization unit containing a component derived from (a3).
Polymer (II); modification in which an unsaturated bond, which is a component derived from an unsaturated monomer (a4) having a functional group capable of reacting with an acid group, is introduced into the side chain of the polymerization unit of the copolymer of (I) polymer.
Polymer (III); a polymerization unit in a copolymer having a polymerization unit containing the component derived from the above (a1), the component derived from the above (a4), and the component derived from the above (a3) optionally used The modified polymer in which the unsaturated bond which is a component derived from unsaturated monobasic acid (a5), and the acid group which is a component derived from polybasic acid or its anhydride (a6) are introduce | transduced into the side chain of these.

(Polymer (I))
The polymer (I) is a component derived from the monomer (a1) having a C10-C20 crosslinked cyclic hydrocarbon group, a component derived from the unsaturated acid monomer (a2), and other components optionally used. It is a copolymer which has a polymerization unit containing the component derived from a monomer (a3).

"C10-C20 bridged cyclic hydrocarbon group monomer (a1)"
The monomer (a1) having a C10 to C20 bridged cyclic hydrocarbon group which is used as a raw material of the polymer (I) and which is a constituent component of the polymer (I) is a C10 to C20 bridged ring type It is preferable that it is (meth) acrylate which has a hydrocarbon group.
As used herein, “(meth) acrylate” means acrylate or methacrylate, or both of them.

  The monomer (a1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms is more preferably a (meth) acrylate having a structure represented by the above formula (3) and / or the formula (4) It is more preferable that it is an adamantyl (meth) acrylate and / or a (meth) acrylate having a structure represented by the following formula (5).

（式（５）中、Ｒ^６〜Ｒ^８はそれぞれ独立に水素原子またはメチル基を表す。Ｒ^９、Ｒ^１０はそれぞれ独立に水素原子もしくはメチル基、又は互いに連結した飽和もしくは不飽和の環を表す。＊は（メタ）アクリロイルオキシ基（ＣＨ_２＝ＣＨＣＯＯ−またはＣＨ_２＝Ｃ（ＣＨ_３）ＣＯＯ−）に連結される結合手を表す。

(In formula (5), R ^{6 to} R ⁸ each independently represent a hydrogen atom or a methyl group. R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group, or a saturated or unsaturated ring linked to each other. * Represents a bond linked to a (meth) acryloyloxy group (CH ₂ = CHCOO- or CH ₂ = C (CH ₃ ) COO-).

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

  Specific examples of the (meth) acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate and isobornyl (meth) acrylate, Any one or more kinds of (meth) acrylates selected from adamantyl (meth) acrylates may be mentioned, and dicyclopentanyl methacrylate is preferable. When the polymer (I) has a component derived from dicyclopentanyl methacrylate, the resin cured film made of the cured product of the photosensitive resin composition containing the polymer (I) has heat decomposition resistance and heat yellowing resistance It will be good.

"Unsaturated acid monomer (a2)"
The unsaturated acid monomer (a2) which is used as a raw material of the polymer (I) and which is a component of the polymer (I) has a polymerizable unsaturated bond and an acid group. The resin cured film which consists of hardened | cured material of the photosensitive resin composition containing polymer (I) as a polymer (I) having a component derived from unsaturated acid monomer (a2) is unsaturated acid monomer (a2). Good developability is obtained by the acid group derived from).
The unsaturated acid monomer (a2) may be a monomer having a polymerizable unsaturated bond and an acid group, and is selected, for example, from unsaturated carboxylic acids or their anhydrides, unsaturated sulfonic acids and unsaturated phosphonic acids Any one or more monomers are exemplified.

  Specifically, as the unsaturated acid monomer (a2), (meth) acrylic acid, α-bromo (meth) acrylic acid, β-furyl (meth) acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α- Cyanocinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic acid, citraconic acid, unsaturated carboxylic acids such as citraconic acid or anhydrides thereof Unsaturated sulfonic acids such as 2-acrylamido-2-methylpropane sulfonic acid, tert-butyl acrylamido sulfonic acid, p-styrene sulfonic acid and the like; unsaturated phosphonic acids such as vinyl phosphonic acid;

Among these, particularly as the unsaturated acid monomer (a2), a polymer (I) having a carboxy group is obtained, and therefore, unsaturated carboxylic acids or anhydrides thereof are preferable, and (meth) acrylic acid is particularly preferable.
As used herein, “(meth) acrylic” means acrylic or methacrylic or both of them.

  The polymer (I) may be a copolymer containing a component derived from the monomer (a1) having a C 10 -C 20 crosslinked cyclic hydrocarbon group and a component derived from the unsaturated acid monomer (a 2) It may be a copolymer containing the above-mentioned components derived from the monomers (a1) and (a2) and one or more other components derived from the monomer (a3).

"Other monomer (a3)"
The other monomer (a3) which is used as a raw material of the polymer (I) and is a component of the polymer (I) is a monomer (a1) having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms, an unsaturated acid Monomer (a2), unsaturated monomer (a4) having a functional group capable of reacting with an acid group, unsaturated monobasic acid (a5), monomer other than polybasic acid or its anhydride (a6), specifically, Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Aromatic vinyl compounds such as methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene and the like;

  Norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene And cyclic olefins having a norbornene structure; dienes such as butadiene, isoprene and chloroprene;

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso-butyl (meth) Acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl ( Meta) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, 1,4-cyclohexene Dimethanol mono (meth) acrylate, norbornyl (meth) acrylate, 5-methyl norbornyl (meth) acrylate, 5-ethyl norbornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1- Trifluoroethyl (meth) acrylate, Perfluoroethyl (meth) acrylate, Perfluoro-n-propyl (meth) acrylate, Perfluoro-isopropyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) (Meth) acrylic acid esters having no aromatic ring such as acrylates;

  Benzyl (meth) acrylate, rosin (meth) acrylate, triphenylmethyl (meth) acrylate, phenyl (meth) acrylate, cumyl (meth) acrylate, 4-phenoxyphenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene (Meth) acrylic acid esters having an aromatic ring such as glycol (meth) acrylate, nonyl phenoxy polyethylene glycol mono (meth) acrylate, biphenyl oxyethyl (meth) acrylate, naphthalene (meth) acrylate, anthracene (meth) acrylate;

  (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic acid amides such as N-di-isopropylamide, (meth) acrylic acid anthracenylamide; (meth) acrylic acid anilide, (meth) acrylic acid (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, fluorine Vinyl compounds such as vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene; diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itaconate, etc. unsaturated dicarboxylic acid diesters; N-phenylmaleimide, N -Cyclohexylmaleimide, N-lauryl Reimido, mono maleimides such as N-(4-hydroxyphenyl) maleimide; and the like.

Among these, the other monomer (a3) is preferably one or more selected from an aromatic vinyl compound, a cyclic olefin having a norbornene structure, and an aromatic (meth) acrylate.
The resin cured film which consists of hardened | cured material of the photosensitive resin composition containing polymer (I) as polymer (I) has a structural component derived from an aromatic vinyl compound has favorable heat-resistant degradability and pigment dispersibility The Moreover, the resin cured film which consists of hardened | cured material of the photosensitive resin composition containing polymer (I) that polymer (I) has a structural component derived from the cyclic olefin which has a norbornene structure has favorable heat-resistant decomposition resistance , Heat resistant yellowing and pigment dispersibility. Moreover, the resin cured film which consists of hardened | cured material of the photosensitive resin composition containing polymer (I) as a polymer (I) having a component derived from the (meth) acrylic acid ester which has aromatic is favorable. It has a good pigment dispersibility.

The content of the component derived from the above-mentioned monomer (a1) (a2) (a3) in the polymer (I) is the ratio of the monomer (a1) (a2) (a3) used as the raw material of the polymer (I) Consider the same.
The content of the component derived from the crosslinked cyclic hydrocarbon group monomer (a1) having 10 to 20 carbon atoms in the polymer (I) is preferably 1 to 90 mol%, and is 2 to 80 mol%. It is more preferable that it is 3-70 mol%. The resin cured film which consists of hardened | cured material of the photosensitive resin composition containing polymer (I) as content of the structural component derived from a monomer (a1) is the said range becomes a more favorable thing of heat resistance.

  The content of the component derived from the unsaturated acid monomer (a2) in the polymer (I) is preferably 10 to 99 mol%, more preferably 15 to 98 mol%, and 20 to 97 mol% It is further preferred that When the content of the component derived from the monomer (a2) is in the above range, the developing speed in the case of alkali development of a resin cured film made of a cured product of the photosensitive resin composition containing the polymer (I) becomes appropriate. Good developability is obtained.

  The content of the component derived from the other monomer (a3) in the polymer (I) is preferably 0 to 80 mol%, more preferably 5 to 70 mol%, and 10 to 65 mol%. It is further preferred that By containing 80 mol% or less of the component derived from the monomer (a3), the pigment dispersibility of the polymer (I), the heat resistance of the cured resin film comprising the cured product of the photosensitive resin composition containing the polymer (I), etc. The characteristics can be appropriately improved.

(Method of producing polymer (I))
The polymer (I) is, 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) optionally used. Can be produced by a method of copolymerization according to a conventionally known radical polymerization method.
The copolymerization reaction for producing the polymer (I) may be carried out in the presence of a solvent. For example, the above monomers (a1) and (a2) and optionally used (a3) are dissolved in a solvent, and a polymerization initiator is added to the solution obtained, and the reaction is carried out at 50 to 130 ° C. for 1 to 20 hours The polymer (I) can be produced by the method of copolymerization reaction.

  The solvent (polymerizing solvent) used when producing the polymer (I) is not particularly limited as long as it is inactive in the polymerization reaction, and for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl 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 , Dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, (poly) alkylene glycol monoalkyl ether such as tripropylene glycol monoethyl ether;

  (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, Other ethers such as tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

  Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate , N-propyl butyrate, i-propyl butyrate, n-butyrate Le, methyl pyruvate, ethyl pyruvate, pyruvate n- propyl, methyl acetoacetate, ethyl acetoacetate, esters such as ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene; Carboxylic acid amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like. These solvents may be used alone or in combination of two or more.
Among these polymerization solvents, glycol ether solvents are preferable, and (poly) alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate are particularly preferable. Is preferred.

  The use amount of the polymerization solvent used when producing the polymer (I) is not particularly limited, but is generally 30 to 1,000 parts by mass, preferably 100 parts by mass in total of the charged amount of the raw material monomers. Is 50 to 800 parts by mass. When the amount of the solvent used is 1,000 parts by mass or less, the decrease in molecular weight of the polymer (I) due to the chain transfer action can be suppressed, and the viscosity of the polymer (I) can be controlled within an appropriate range. Further, by setting the amount of the solvent to be 30 parts by mass or more, an abnormal polymerization reaction can be prevented, the polymerization reaction can be stably performed, and coloring and gelation of the polymer (I) can be prevented.

Examples of the polymerization initiator used for the copolymerization reaction for producing the polymer (I) include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2-ethylhexano There is no particular limitation, and it is not particularly limited. These polymerization initiators can be used alone or in combination of two or more.
The use amount of the polymerization initiator is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass with respect to 100 parts by mass in total of the charged amount of the monomer.

(Polymer (II))
In the polymer (II), an unsaturated bond which is a component derived from an unsaturated monomer (a4) having a functional group capable of reacting with an acid group is introduced into the side chain of the polymer unit of the copolymer which is the polymer (I) Modified polymers. In the polymer (II), since the unsaturated bond is introduced into the side chain of the polymerization unit of the copolymer which is the polymer (I), the photosensitive resin composition containing the polymer (II) has high sensitivity. .

"Unsaturated monomer (a4) having a functional group that reacts with an acid group"
The unsaturated monomer (a4) having a functional group to be reacted with an acid group, which is used as a raw material of the polymer (II) and is a component of the polymer (II), may be only one type, or two or more types The unsaturated compound is preferably an unsaturated compound having a functional group that reacts with an acid group such as an epoxy group, a hydroxy group, an amino group or a vinyl ether group.

  Specifically, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate having an alicyclic epoxy, and its lactone adduct as an unsaturated monomer (a4) having a functional group that reacts with an acid group (Eg, Daicel Chemical Industries, Ltd. Cyclomer A200, M100), mono (meth) acrylic acid ester of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, dicyclopentenyl (meth) Radically polymerizable monomers having an epoxy group such as acrylate acrylates, dicyclopentenyl oxyethyl (meth) acrylate epoxides; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Radical polymerization having a hydroxy group such as meta) acrylate, 6-hydroxyhexyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, allyl alcohol and the like Monomers; radically polymerizable monomers having an amino group such as 4-aminostyrene; radically polymerizable monomers having a vinyl ether group such as 2-vinyloxyethoxyethyl (meth) acrylate and the like.

  Among the unsaturated monomers (a4) having a functional group that reacts with these acid groups, it is preferable to use a radically polymerizable monomer having an epoxy group, and glycidyl (meth) acrylate is particularly preferable. When a radically polymerizable monomer having an epoxy group is used as the unsaturated monomer (a4) having a functional group capable of reacting with an acid group, the composition derived from the unsaturated acid monomer (a2) when producing the polymer (II) An unsaturated bond can be easily introduced into the side chain of the copolymer (I) by reaction with the acid group (component).

The content of the component derived from the above-mentioned monomer (a1) (a2) (a3) (a4) in the polymer (II) is the same as that of the monomer (a1) (a2) (a3) used as a raw material of the polymer (II) It is considered to be the same as the ratio of (a4).
The preferred range of the content of the component derived from the above-mentioned monomer (a1) (a2) (a3) in the polymer (II) is that from the above-mentioned monomer (a1) (a2) (a3) in the polymer (I) It is the same as the content of the component.

  The content of the component derived from the unsaturated monomer (a4) having a functional group capable of reacting with an acid group in the polymer (II) is preferably 1 to 95 mol%, and preferably 3 to 75 mol%. It is more preferable that it is 5 to 55 mol%. The photosensitive resin composition containing a polymer (II), ensuring content of a constituent component derived from a monomer (a1) (a2) (a3) as content of a constituent component derived from a monomer (a4) is the said range The sensitivity of objects can be increased.

(Method of producing polymer (II))
The polymer (II) is prepared by reacting the copolymer which is the polymer (I) with the unsaturated monomer (a4) having a functional group that reacts with an acid group by a conventionally known method, to the side chain of the copolymer It can manufacture by the method of setting it as the modified polymer which introduce | transduced the polymerizable unsaturated bond.
Specifically, for example, a copolymer which is a polymer (I), an unsaturated monomer (a4) having a functional group which reacts with an acid group, a polymerization inhibitor, and a catalyst are added to a reaction solvent; The polymer (II) can be produced by the method of modifying reaction at ̃150 ° C., preferably 80 ̃130 ° C.
In the modification reaction for producing the polymer (II), there is no particular problem even if the solvent used in the copolymerization reaction for producing the polymer (I) is contained. For this reason, after the copolymerization reaction for producing the polymer (I) is completed, the modification reaction for producing the polymer (II) can be carried out without removing the solvent.

The polymerization inhibitor used to prevent gelation when producing the polymer (II) is not particularly limited, and examples thereof include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether and the like.
Also, the catalyst used when producing the polymer (II) is not particularly limited, but, for example, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzyl ammonium chloride, triphenylphosphine Such as phosphorus compounds and chromium chelate compounds.

(Polymer (III))
The polymer (III) is a component derived from a monomer (a1) having a C 10 -C 20 crosslinked cyclic hydrocarbon group, and a component derived from an unsaturated monomer (a 4) having a functional group that reacts with an acid group. And an unsaturated component which is a component derived from unsaturated monobasic acid (a5) in a side chain of a polymerized unit in a copolymer having a polymerized unit containing a component derived from another monomer (a3) optionally used. It is a modified polymer into which a bond and an acid group which is a component derived from a polybasic acid or its anhydride (a6) are introduced.

  In the polymer (III), the side chain of the copolymer containing the component derived from the monomer (a1), the component derived from the (a4), and the component derived from the other monomer (a3) optionally used, Since the unsaturated bond is introduced, the sensitivity of the photosensitive resin composition containing the polymer (III) is high. Further, in the polymer (III), since an acid group is introduced into the above-mentioned side chain, a resin cured film composed of a cured product of the photosensitive resin composition containing the polymer (III) has good developability.

  As the above-mentioned monomers (a1) and (a3) which are used as a raw material of the polymer (III) and which is a component of the polymer (III), the above monomers (a1) and (a3) which are components of a polymer (I) are used The same one can be used. Moreover, as said monomer (a4) used as a raw material of polymer (III) and used as a structural component of polymer (III), the same thing as said monomer (a4) used as a structural component of polymer (II) is used be able to.

  As the above-mentioned monomer (a4) to be a component of the polymer (III), among the monomers used as the above-mentioned monomer (a4) to be a component of the polymer (II), use is made of a radically polymerizable monomer having an epoxy group. Are preferred, and glycidyl (meth) acrylate is particularly preferred. When a radically polymerizable monomer having an epoxy group is used as the unsaturated monomer (a4) having a functional group capable of reacting with an acid group, the side chain of the copolymer which is a precursor of the polymer (III) described later is easy Can introduce unsaturated bonds and acid groups.

"Unsaturated monobasic acid (a5)"
Examples of the unsaturated monobasic acid (a5) which is used as a raw material of the polymer (III) and which is a component of the polymer (III) include (meth) acrylic acid, α-bromo (meth) acrylic acid, β-furyl As unsaturated acid monomer (a2) such as unsaturated carboxylic acid such as (meth) acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate There is one that can be used.

"Polybasic acid or its anhydride (a6)"
As a polybasic acid or its anhydride (a6) which is used as a raw material of the polymer (III) and which is a component of the polymer (III), maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid Unsaturated carboxylic acids such as acid, citraconic anhydride or the anhydrides thereof; unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, p-styrenesulfonic acid, vinylphosphonic acid and the like And unsaturated polybasic acids exemplified as unsaturated acid monomers (a2) such as, and anhydrides thereof.

The polybasic acid or its anhydride (a6) to be a component of the polymer (III) may be a non-polymerizable unsaturated polybasic acid and its anhydride, a saturated polybasic acid and its anhydride. For example, malonic acid, succinic acid, glutaric acid, adipic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid Examples thereof include acids, dibasic acids such as phthalic acid, tribasic acids such as trimellitic acid, tetrabasic acids such as pyromellitic acid, and anhydrides thereof.
Among these, dicarboxylic acid anhydride is preferably used as the polybasic acid or its anhydride (a6).

  The content of the component derived from the above-mentioned monomer (a1) (a3) (a4), unsaturated monobasic acid (a5), polybasic acid or its anhydride (a6) in the polymer (III) It can be considered to be the same as the ratio of the monomers (a1) (a3) (a4), the unsaturated monobasic acid (a5), the polybasic acid or the anhydride (a6) used as the raw material of III).

  The content of the component derived from the crosslinked cyclic hydrocarbon group monomer (a1) having 10 to 20 carbon atoms in the polymer (III) is preferably 1 to 80 mol%, and is 2 to 70 mol%. Is more preferable, and 3 to 60 mol% is more preferable. The resin cured film which consists of hardened | cured material of the photosensitive resin composition containing polymer (III) as content of the structural component derived from a monomer (a1) is the said range becomes a more favorable thing of heat resistance.

  The content of the component derived from the unsaturated monomer (a4) having a functional group that reacts with an acid group in the polymer (III) is preferably 20 to 98 mol%, and is 25 to 84 mol% More preferably, it is 30 to 70 mol%. When the content of the component derived from the monomer (a4) is in the above range, an appropriate amount of unsaturated group can be introduced into the side chain of the precursor in the step of producing the polymer (III), The sensitivity of the cured resin film made of the cured product of the photosensitive resin composition containing the resin composition is further improved.

  The content of the component derived from the other monomer (a3) in the polymer (III) is preferably 0 to 80 mol%, more preferably 5 to 70 mol%, and 10 to 60 mol%. It is further preferred that By containing 80 mol% or less of the component derived from the monomer (a3), the pigment dispersibility of the polymer (III), the heat resistance of the cured resin film comprising the cured product of the photosensitive resin composition containing the polymer (III), etc. The characteristics can be appropriately improved.

  The content of the component derived from the unsaturated monobasic acid (a5) in the polymer (III) is preferably 20 to 98 mol%, more preferably 25 to 84 mol%, and 30 to 70 mol. More preferably, it is%. The sensitivity of the resin cured film which consists of hardened | cured material of the photosensitive resin composition containing polymer (III) as content of the structural component derived from unsaturated monobasic acid (a5) is the said range becomes more favorable.

  The content of the component derived from the polybasic acid or its anhydride (a6) in the polymer (III) is preferably 16 to 78 mol%, more preferably 20 to 67 mol%, and 24 to More preferably, it is 56 mol%. Development at the time of carrying out alkali development of the resin cured film which consists of hardened | cured material of the photosensitive resin composition containing polymer (III) as content of the structural component derived from polybasic acid or its anhydride (a6) is the said range The speed is appropriate and better developability can be obtained.

(Method of producing polymer (III))
As a method of manufacturing 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 capable of reacting with an acid group, and other monomers (a3) optionally used The copolymer is copolymerized according to a conventionally known radical polymerization method to produce a precursor consisting of a copolymer.
The precursor to be the polymer (III) is a polymer obtained by replacing the unsaturated acid monomer (a2) used when producing the polymer (I) with the unsaturated monomer (a4) having a functional group that reacts with an acid group It can manufacture by the method similar to the manufacturing method of (I).

Thereafter, the precursor, the unsaturated monobasic acid (a5), and the polybasic acid or its anhydride (a6) are reacted to introduce an acid group and a polymerizable unsaturated bond in the side chain of the precursor. It can be produced by the method of making it a polymer.
Specifically, for example, a precursor which is a copolymer, an unsaturated monobasic acid (a5), a polybasic acid or its anhydride (a6), a polymerization inhibitor, and a catalyst are added to a reaction solvent. The polymer (III) can be produced by a modification reaction at 50 to 150 ° C., preferably 80 to 130 ° C.

When a copolymer of an unsaturated monomer having an epoxy group is produced as a precursor using a radically polymerizable monomer having an epoxy group as the monomer (a4) which is a raw material of the polymer (III), the following modification reaction Will occur.
When the precursor is reacted with the unsaturated monobasic acid (a5), the epoxy group present in the molecule of the precursor is cleaved to introduce an unsaturated bond into the side chain of the precursor, and at the same time, a hydroxy group is formed. . The generated hydroxy group is reacted with the polybasic acid or its anhydride (a6) to introduce an acid group on the side chain of the precursor.

In addition, a copolymer having a hydroxy group as a precursor and a copolymer of an unsaturated monomer having a hydroxy group as a precursor are used as any one or more of the monomers (a1) (a3) (a4) which are raw materials of the polymer (III) The following denaturation reaction occurs.
When the precursor, the unsaturated monobasic acid (a5) and the polybasic acid or its anhydride (a6) are reacted, the hydroxy group present in the molecule of the precursor and the unsaturated monobasic acid (a5) And a polybasic acid or its anhydride (a6) reacts, and an unsaturated bond and an acid group are introduce | transduced to the side chain of a precursor.

  In the present embodiment, as the polymer (A), the polymer shown in the above (I), (II) or (III) is described as an example, but the polymer (A) in the present invention has acid groups and carbon numbers It may be a polymer having 10 to 20 bridged cyclic hydrocarbon groups, and is not limited to the polymers shown in the above (I), (II) or (III).

  The method of producing the polymer (A) is not limited to the method of producing the polymer (I) (II) (III) described above, for example, using the production method shown in the following (1) or (2) It is also good.

(1) A copolymer precursor is produced by the method of copolymerizing the above-mentioned monomer (a1) and an unsaturated monomer containing an epoxy group. Thereafter, the precursor and polybasic acid anhydride are reacted to cleave the epoxy group present in the molecule of the precursor, thereby introducing an acid group to the side chain of the precursor and simultaneously forming a hydroxy group. Thereafter, a hydroxyl group generated in a precursor having an acid group in a side chain is reacted with an isocyanate compound containing an unsaturated bond such as 2- (meth) acryloyloxyethyl isocyanate or 2- (meth) acryloyl ethyl isocyanate. , Introduce unsaturated bonds into the side chains of the precursors.

(2) The precursor which consists of a copolymer is manufactured by the method of copolymerizing the said monomer (a1) and the unsaturated monomer containing a hydroxyl group. Thereafter, a hydroxy group present in the molecule of the precursor, a polybasic acid anhydride and an isocyanate compound containing an unsaturated bond are reacted to introduce an acid group and an unsaturated bond to the side chain of the precursor.

(Compound (B))
The compound (B) contains a hydroxy group or an acid group, and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms. As the compound (B), one not containing an ethylenically unsaturated double bond in the structure is preferable. The resin composition of the present embodiment contains the compound (B), and thus has excellent storage stability.

As an acid group contained in a compound (B), the same thing as the acid group which a polymer (A) has can be used, for example. Specifically, examples of the acid group contained in the compound (B) include carboxy group (-COOH), sulfo group (-SO ₃ H), phosphoric acid group (-PO (OH) ₂ ), etc. Particularly preferred is a carboxy group. The polymer (B) may have only one type of acid group, or two or more types of acid groups. The number of acid groups possessed by the polymer (B) may be only one or two or more.

As a C10-C20 bridged cyclic hydrocarbon group in a compound (B), the same thing as the C10-C20 bridged cyclic hydrocarbon group which the polymer (A) mentioned above has can be used .
The C10-C20 bridged cyclic hydrocarbon group contained in the compound (B) in the resin composition of this embodiment and the C10-C20 bridged cyclic hydrocarbon contained in the polymer (A) The groups may be the same or different and are preferably the same. When producing a resin composition in which a C10-C20 bridged cyclic hydrocarbon group is the same between the compound (B) and the polymer (A), a polymerization reaction was carried out to produce the polymer (A) Preferably, not only the polymer (A) but also the compound (B) is contained in the polymerization system. Specifically, a method of selecting one containing compound (B) as a raw material of polymer (A) and / or a method of forming compound (B) by a polymerization reaction for producing polymer (A) can be used . In this case, a polymerization system which has undergone a polymerization reaction to produce the polymer (A) can be used as it is as a resin composition of the present embodiment containing the polymer (A) and the compound (B).

  The C10 to C20 bridged cyclic hydrocarbon group contained in the compound (B) is a group corresponding to the remaining part of the C10 to C20 bridged cyclic hydrocarbon after removing one hydrogen atom It is. The skeleton of the bridged cyclic hydrocarbon in the 10 to 20 carbon bridged cyclic hydrocarbon group possessed by the compound (B) is the same as the bridged cyclic hydrocarbon group possessed by the polymer (A), 3) It is preferable that it is a structure represented by (4), and, specifically, it is more preferable that it is a structure represented by following (6).

（式（６）中、Ｒ^１１〜Ｒ^１３はそれぞれ独立に水素原子またはメチル基を表す。Ｒ^１４、Ｒ^１５はそれぞれ独立に水素原子もしくはメチル基、又は互いに連結した飽和もしくは不飽和の環を表す。＊は化合物（Ｂ）に含まれる結合手を表す。）

(In formula (6), R ^{11 to} R ¹³ each independently represent a hydrogen atom or a methyl group. R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a methyl group, or a saturated or unsaturated ring linked to each other. * Represents a bond included in compound (B).)

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

As the compound (B), specifically, a reaction product of an alcohol selected from dicyclopentenyl alcohol, dicyclopentanyl alcohol, isobornyl alcohol, adamantyl alcohol, and these alcohols and polybasic acid anhydrides One or more selected or the like can be mentioned. These compounds can be used alone or in combination of two or more as the compound (B).
Among the above compounds, the compound (B) is, in particular, dicyclopentanyl alcohol represented by the following formula (7) and / or dicyclopentacycle represented by the following formula (8) from the viewpoint of storage stability and the like. It is preferred to use the reaction product of a nyl alcohol and a polybasic acid anhydride.

（式（８）中、Ｒは２価の連結基である。）

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

  The compound (B) in the resin composition may be intentionally added to the resin composition, or a polymerization system in which a part or all of the polymerization reaction has been carried out to produce the polymer (A). It may be brought in from That is, the compound (B) is subjected to a polymerization reaction to produce a polymer (A) from a monomer (a1) having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms, which is a raw material of the polymer (A). It may be one introduced into the polymerization system carried out and / or one 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, and 0.001 to 1 mass of the total of 100 parts by mass of the polymer (A) and the compound (B). It is 1.0 part by mass, preferably 0.005 to 0.7 parts by mass, and more preferably 0.01 to 0.5 parts by mass.
The storage stability of a resin composition becomes favorable for content of said compound (B) to be 0.001 mass part or more. It becomes a resin composition which fully contains a polymer (A) as content of said compound (B) is 1.0 mass part or less. For this reason, the resin cured film which is a cured product of the photosensitive resin composition containing a resin composition has excellent heat resistance and developability.

(Solvent (C))
The resin composition of the present embodiment contains the above-described polymer (A) and the compound (B), and may contain a solvent (C) as required.
As the solvent (C), any inert solvent which does not react with the polymer (A) may be used, and for example, the above-mentioned solvent (polymerization solvent) used when producing the polymer (A) can be used, In particular, (poly) alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate are preferable.

(Reactive diluent (D))
The resin composition of the present embodiment may contain a reactive diluent (D) as necessary. By containing the reactive diluent (D), the viscosity of the resin composition is adjusted to improve the processability, or the strength of the cured product of the resin composition and / or the adhesion to the substrate are improved. Can.

  As the reactive diluent (D), a compound having at least one polymerizable ethylenic unsaturated group as a polymerizable functional group in the molecule is used, and in particular, it is preferable to use a compound having a plurality of polymerizable functional groups . However, the reactive diluent (D) does not contain the compound (B). Specifically, monofunctional monomers and / or polyfunctional monomers shown below can be used as the reactive diluent (D).

  Examples of monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide and 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 , 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydric acid Rofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, half (meth) of phthalic acid derivative (Meth) acrylates such as acrylates; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene and vinyltoluene; and carboxylic acid esters such as vinyl acetate and vinyl propionate. These monofunctional monomers can be used alone or in combination of two or more.

  As polyfunctional monomers, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di ( Meta) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2 Bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate Ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth 2.) Reactants of acrylate (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate, hexamethylene diisocyanate etc. with 2-bihydroxyethyl (meth) acrylate (Meth) acrylates such as tri (meth) acrylate of tris (hydroxyethyl) isocyanurate; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, diallyl benzene phosphonate; dicarboxylic acid esters such as divinyl adipate; Rucyanurate, methylene bis (meth) acrylamide, (meth) acrylamido methylene ether, a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, etc. may be mentioned. These polyfunctional monomers can be used alone or in combination of two or more.

  Among the above monomers, as the reactive diluent (D), any one of trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate Is preferred.

When the resin composition of the present embodiment contains the polymer (A), the compound (B) and the solvent (C) described above, and optionally contains the reactive diluent (D), each component The content of A), (B), (C), and (D) can be appropriately selected according to the purpose of use of the resin composition, and is preferably in the range described below.
The content of the polymer (A) in the resin composition is 10 to 100 parts by mass with respect to 100 parts by mass in total of the polymer (A), the compound (B) and the reactive diluent (D). It is preferable, it is more preferable that it is 20-80 mass parts, and it is further more preferable that it is 30-75 mass parts.

  The content of the solvent (C) in the resin composition is 30 to 1,000 parts by mass with respect to 100 parts by mass in total of the polymer (A), the compound (B) and the reactive diluent (D). It is preferable that it is 50-800 mass parts, It is more preferable that it is 100-700 mass parts.

The content of the reactive diluent (D) in the resin composition is 0 to 90 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 a part, more preferably 20 to 80 parts by mass, and still 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. preferable.

  A resin composition having an appropriate viscosity when the contents of the polymer (A), the compound (B), the solvent (C) and the reactive diluent (D) in the resin composition are respectively in the above ranges It becomes. Therefore, it is suitable as a material of the photosensitive resin composition mentioned later, and can be suitably used also as materials, such as various coating agents, adhesives, and a binder for printing inks.

(Method for producing resin composition)
The resin composition of the present embodiment is, for example, a known mixing device including the polymer (A) and the compound (B) described above, and a solvent (C) and a reactive diluent (D) which are optionally used. It can be produced by mixing using
When manufacturing the resin composition of this embodiment, the polymer (A) isolated from the polymerization system which performed the polymerization reaction in order to manufacture a polymer (A) can be used as a polymer (A).

Moreover, when manufacturing the resin composition of this embodiment, the polymer (A) contained in the polymerization system which performed the polymerization reaction in order to manufacture a polymer (A), and a polymer (A) are manufactured. You may use the solvent used in the case as it is as a raw material of a resin composition. In this case, as a solvent (C) used as a raw material of a resin composition, in addition to the solvent used at the time of manufacturing a polymer (A), you may further add a desired solvent as needed. Moreover, the solvent added with the raw material of resin compositions other than a solvent (C) may be contained in the solvent (C) which is a raw material of a resin composition.
When not only the polymer (A) but also the compound (B) is contained in the polymerization system in which the polymerization reaction was carried out to produce the polymer (A), the polymerization reaction to produce the polymer (A) The polymerization system which carried out may be used as it is as a resin composition of this embodiment containing a polymer (A) and a compound (B).

The resin composition of the present embodiment comprises a polymer (A) having an acid group and a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms, and a hydroxy group or an acid group and a crosslinked cyclic system having 10 to 20 carbon atoms. It contains a compound (B) containing a hydrocarbon group and a specific ratio. For this reason, the resin composition of this embodiment is suitable as a material of the photosensitive resin composition which can obtain the resin cured film which has the outstanding developability, and has the outstanding storage stability.
Moreover, since the resin composition of this embodiment has the outstanding storage stability, it is suitable as materials, such as various coating agents, an adhesive agent, and a binder for printing inks.

[2. Photosensitive resin composition]
The photosensitive resin composition of the present embodiment contains the resin composition of the present embodiment, a photopolymerization initiator (E), and a colorant (F) optionally contained. The photosensitive resin composition of the present embodiment is polymerized and cured by light irradiation to form a cured product.

(Photoinitiator (E))
The photopolymerization initiator (E) is not particularly limited. For example, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9 Oxime esters such as -ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-and 1- (o-acetyloxime); benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether and the like Benzoines; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) ) Phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dime Acetophenones such as lamino-1- (4-morpholinophenyl) butanone-1; anthraquinones such as 2-methyl anthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone and the like; xanthone, thioxanthone, 2, Thioxanthones such as 4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone And benzophenones such as 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone; acyl phosphine oxides; and the like. These photoinitiators (E) can be used individually or in combination of 2 or more types.

  Among the above compounds, the photopolymerization initiator (E) is particularly high in sensitivity to i-ray (365 nm) and less yellowing of the cured product during curing and baking, so 2-methyl-1- (4) Acetophenones such as -methylthiophenyl) -2-morpholinopropan-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- It is preferable to use oxime ester-based compounds such as [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyl oxime). These photopolymerization initiators can be used alone or in combination of two or more, depending on, for example, the target sensitivity.

(Colorant (F))
As a coloring agent (F), what is melt | dissolved or disperse | distributed to a solvent (C) is used, for example, dye and / or a pigment etc. are mentioned. The colorant (F) may be, for example, only a dye, only a pigment, or may be used, depending on the color of the pixel which is the target product produced using the photosensitive resin composition. You may use it in combination with a pigment. When using a photosensitive resin composition as a material of a color filter, it is preferable to use a dye as a coloring agent (F) by the reason shown below. Pigments are particles, while dyes are molecules. For this reason, when a dye is used as the coloring agent (F), scattering of light in the color filter is suppressed and the brightness of the image display device provided with the color filter is increased as compared with the case where a pigment is used. .

  As the dye, from the viewpoints of solubility in the solvent (C) and the alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance of the photosensitive resin composition, etc., carboxylic acid, sulfonic acid, etc. It is preferable to use an acid dye having an acid group, a salt of an acid dye with a nitrogen compound, a sulfonamide of an acid dye, and the like. In particular, it is preferable to use anthraquinone dyes, azo dyes, xanthene dyes, anthraquinone dyes or phthalocyanine dyes as the dye. Among them, it is particularly preferable to use one or both of an anthraquinone dye and a xanthene dye, since the photosensitive resin composition can provide a cured resin film having a high transmittance.

  Specifically, as a dye, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92 , Acid 113, 120, 129, 147; acid chrome violet K; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56 63, 74, 95; acid red 1, 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, 13 138, 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 yellow 3, VALIFAST BLUE 1603, 1605, 1621, 2606, 2620, 2670 and derivatives thereof. These dyes can be used alone or in combination of two or more, depending on, for example, the color of the target pixel.

  As a pigment, C.I. I. Pigment 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, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; I. Orange pigments such as C.I. pigment oranges 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; I. Pigment red 9, 97, 105, 122, 123, 144, 149, 154, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. A pigment; C.I. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60, etc .; blue pigments such as C.I. I. Violet pigments such as CI pigment violet 1, 19, 23, 29, 32, 36, 38, etc .; I. Green pigments such as CI pigment green 7, 36, 58, 59, 62; I. Brown pigments such as C.I. pigment brown 23, 25; I. Pigment blacks 1 and 7, carbon black, titanium black, black pigments such as iron oxide, and the like. These pigments can be used alone or in combination of two or more, depending on, for example, the color of the target pixel.

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 a dispersing agent, it is preferable to use the polymeric dispersing agent which is excellent in the dispersion stability over time. As a polymer dispersant, a urethane type dispersant, a polyethyleneimine type dispersant, a polyoxyethylene alkyl ether type dispersant, a polyoxyethylene glycol diester type dispersant, a sorbitan aliphatic ester type dispersant, an aliphatic modified ester type dispersion Agents and the like. As the polymer dispersant, it is commercially available under the trade name of EFKA (manufactured by F-KA Chemical's BV (EFKA)), Disperbyk (manufactured by BIC-Chemie), Disparon (manufactured by Kushimoto Chemical Co., Ltd.), SOLSPERSE (manufactured by ZENECA), etc. You may use what you have.
The content of the dispersant in the photosensitive resin composition can be appropriately set in accordance with the type of pigment and the like used.

  The photosensitive resin composition of the present embodiment contains the polymer (A), the compound (B), the solvent (C), the reactive diluent (D), and the photopolymerization initiator (E) described above, if necessary. The content of each component ((A), (B), (C), (D), (E), (F)) in the case of containing the coloring agent (F) to be used is the purpose of use of the photosensitive resin composition. It can be selected as appropriate, and is preferably within the range described below.

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

The content of the compound (B) in the photosensitive resin composition is 0.001 to 1.0 parts by mass with respect to 100 parts by mass of the total amount of the polymer (A) and the compound (B). The amount is preferably 0.005 to 0.7 parts by mass, and more preferably 0.01 to 0.5 parts by mass.
The content of the solvent (C) in the photosensitive resin composition is 30 to 1,000 with respect to 100 parts by mass in total of the polymer (A), the compound (B) and the reactive diluent (D). It is preferable that it is a mass part, It is more preferable that it is 50-800 mass parts, It is further more preferable that it is 100-700 mass parts.

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

The content of the photopolymerization initiator (E) in the photosensitive resin composition is 0. 0. relative to 100 parts by mass of the total amount of the polymer (A), the compound (B) and the reactive diluent (D). The amount is preferably 1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and still more preferably 1 to 15 parts by mass.
The content of the colorant (F) in the photosensitive resin composition is 5 to 80 parts by mass with respect to 100 parts by mass in total of the polymer (A), the compound (B) and the reactive diluent (D). It is preferably part, more preferably 5 to 70 parts by mass, and still more preferably 10 to 60 parts by mass.

The contents of the polymer (A), the compound (B), the solvent (C), the reactive diluent (D), the photopolymerization initiator (E) and the colorant (F) in the photosensitive resin composition are respectively It becomes a curable resin composition which has a suitable photocurability as it is in said range.
Even when the photosensitive resin composition does not contain the colorant (F), the above-mentioned polymer (A), compound (B), solvent (C) and reactive diluent (in the photosensitive resin composition) The contents of D) and the photopolymerization initiator (E) can be set in the above ranges, respectively.

  The photosensitive resin composition of the present embodiment may contain, in addition to the above components, known additives such as a coupling agent, a leveling agent, and a thermal polymerization inhibitor in order to impart predetermined properties. Good. The content of the additive contained in the photosensitive resin composition is not particularly limited as long as the effects of the present invention are not impaired.

(Method of producing photosensitive resin composition)
The photosensitive resin composition of the present embodiment includes, for example, a known mixing device, the resin composition of the present embodiment, a photopolymerization initiator (E), and a colorant (F) optionally contained. It can be produced by mixing using
In the production method of the present embodiment, the above-mentioned polymer (A), compound (B), solvent (C), reactive diluent (D), photopolymerization initiator (E), coloring contained in the photosensitive resin composition The order in which the components of the agent (F) are mixed is not particularly limited. For example, it is obtained after preparing a resin composition containing the polymer (A), the compound (B) and the solvent (C) You may manufacture by the method of mixing a reactive diluent (D), a photoinitiator (E), and a coloring agent (F) with a resin composition.

  Since the photosensitive resin composition of the present embodiment contains the resin composition of the present embodiment, a cured resin film having excellent developability can be obtained, and has excellent storage stability. Therefore, the photosensitive resin composition of the present embodiment is suitable as a resist. In particular, the photosensitive resin composition of the present embodiment is a solid-state imaging device such as a CCD (Charged-coupled devices) or a CMOS (Complementary metal-oxide-semiconductor), an organic EL display, a transparent film incorporated in a liquid crystal display device, and protection It is suitable as a resist used for producing a film, an insulating film, an overcoat, a photo spacer, a black matrix, a black column spacer, a color filter and the like.

[3. Cured resin film]
The resin cured film of the present embodiment is a cured product of the photosensitive resin composition of the present embodiment. The resin cured film of this embodiment can be suitably used as a material of a color filter. Hereinafter, a color filter using the resin cured film of the present embodiment will be described as an example of the resin cured film of the present embodiment.

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, the pixels and the black matrix And a protective film formed thereon. The color filter of this embodiment has a pixel and a black matrix which consist of hardened | cured material of the photosensitive resin composition of this embodiment.
In the color filter of the present embodiment, a known configuration can be adopted as a configuration other than the pixels and the 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 polyamide substrate, a polyamide imide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, and the like can be used as appropriate. .

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

The method for applying the photosensitive resin composition is not particularly limited, but screen printing, roll coating, curtain coating, spray coating, spin coating, etc. can be used.
After application of the photosensitive resin composition, if necessary, the solvent (C) contained in the photosensitive resin composition is volatilized by heating using heating means such as a circulating oven, an infrared heater, a hot plate, etc. May be The heating conditions are not particularly limited, and can be appropriately set according to the type of photosensitive resin composition to be used. For example, the heating temperature can be 50 ° C. to 120 ° C., and the heating time can be 30 seconds to 30 minutes.

Specifically, as a method of exposing a coating film made of a photosensitive resin composition, the coating film is exposed partially by exposure to active energy rays such as ultraviolet light and excimer laser light through a negative mask. The method is mentioned. The active energy dose to be applied to the coating film may be appropriately selected according to the composition of the photosensitive resin composition, and is preferably, for example, 30 to 2000 mJ / cm ² . The light source used for 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 and the like can be used.

  The aqueous alkaline solution used for developing the exposed coating film is not particularly limited, but aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like; amine compounds such as ethylamine, diethylamine and dimethylethanolamine Aqueous solution of 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 their sulfates, hydrochlorides or p-toluenesulfonates An aqueous solution of a p-phenylenediamine compound or the like can be used. You may add an antifoamer and surfactant to these aqueous alkali solutions as needed.

In this embodiment, it is preferable to develop the exposed coating film using the above-mentioned alkaline aqueous solution, and then wash it with water and dry it.
The conditions for baking the coated film after development are not particularly limited, and heat treatment may be performed depending on the type of photosensitive resin composition to be used. For example, the baking temperature can be 250 ° C. or less, preferably 240 ° C. or less, particularly preferably 230 ° C. or less. For example, the baking time can be 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

  Thus, the steps of coating, exposing, developing and baking the photosensitive resin compositions corresponding to the respective pixels and the black matrix are sequentially repeated. By this, it consists of hardened | cured material of the photosensitive resin composition of this embodiment, and can form each pixel and black matrix which have a desired shape.

The cured resin film of the present embodiment is a cured product of the photosensitive resin composition of the present embodiment having excellent storage stability, and therefore can be manufactured stably.
In the present embodiment, each pixel and the black matrix made of the cured product of the photosensitive resin composition of the present embodiment have been described as an example, but the cured product of the present embodiment is not limited to the above example. For example, a cured product made of a photosensitive resin composition not containing a colorant (F) may be suitably used as an overcoat, a protective film, an insulating film, etc. incorporated in a solid-state imaging device, an organic EL display, or a liquid crystal display. it can.

  In the embodiment described above, the photosensitive resin composition including the resin composition of the present embodiment and the photopolymerization initiator (E) has been described, but instead of the photopolymerization initiator (E), a curing accelerator and It may be a curable resin composition by containing a known epoxy resin. This curable resin composition can form a desired pattern, for example, by applying it on a substrate by an inkjet method and heating it.

[4. Image display element]
The image display element of the present embodiment comprises the cured resin film of the present embodiment. As an image display element of this embodiment, what has a color filter using the resin cured film of this embodiment is mentioned, for example.
Specifically as an image display element of this embodiment, solid-state image sensors, such as CCD and CMOS, an organic EL display, a liquid crystal display, etc. are mentioned.

  For example, when manufacturing a liquid crystal display element as an image display element of the present embodiment, a color filter using the resin cured film of the present embodiment is formed on a first substrate, and then electrodes, spacers, etc. are sequentially formed. Do. Then, an electrode or the like is formed on the second substrate, and the surface of the first substrate on which the color filter is formed and the surface of the second substrate on which the electrode is formed are bonded to face each other. A predetermined amount of liquid crystal may be injected and sealed between the two substrates.

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. The present invention is not limited to the following examples.
"Resin composition"
Examples containing polymer (A) and compound (B) containing a hydroxy group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms by the method shown below The resin compositions of 1 to 9 and Comparative Examples 1 to 4 were produced and evaluated.

Example 1
"Synthesis of polymer (III)"
175.0 g of propylene glycol monomethyl ether acetate as a solvent was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction pipe, and the mixture was stirred while being purged with nitrogen gas and heated to 120 ° C. Next, 66.0 g of dicyclopentanyl methacrylate which is a monomer (a1) having a C 10 -C 20 crosslinked cyclic hydrocarbon group and an unsaturated monomer (a 4) having a functional group which reacts with an acid group A monomer mixture consisting of 85.2 g of glycidyl methacrylate and 10.4 g of styrene as the other monomer (a3), 17.8 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, NOF Corporation) And Perbutyl O) were added dropwise from the dropping funnel into the flask over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 120 ° C. for 2 hours for copolymerization reaction to obtain a first polymer (precursor).

  Next, the inside of the flask is replaced with 6% oxygen gas, and in the flask, 43.2 g of acrylic acid which is unsaturated monobasic acid (a5), 0.6 g of triphenylphosphine as a catalyst, and polymerization inhibition 0.1 g of hydroquinone, which is an agent, was added, and the addition reaction was performed at 120 ° C. for 6 hours to form a second polymer.

Next, 59.3 g of tetrahydrophthalic anhydride which is a polybasic acid or its anhydride (a6) is added to the second polymer, and an addition reaction is carried out at 115 ° C. for 3 hours to obtain a polymer (III) as a polymer (A) It was generated.
The acid value and the weight average molecular weight of the obtained polymer (A) were measured by the methods described below. As a result, the acid value of the solid content of the polymer (A) was 80 mg KOH / g, and the weight average molecular weight was 8,000.

"Acid number"
It is an acid value of the polymer (A) measured according to JIS K 6901: 2008 5.3.2. Specifically, it means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the polymer (A).

"Weight average molecular weight (Mw)"
Weight average molecular weight (Mw) means standard polystyrene equivalent weight average molecular weight measured under the following conditions using gel permeation chromatography (GPC) (Showex (registered trademark) GPC-101 (manufactured by Showa Denko KK)) Means
Column: Showdex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2% by mass tetrahydrofuran solution of copolymer Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Showex (registered trademark) RI-71S) (manufactured by Showa Denko KK)
Flow rate: 1 mL / min

Next, 281.9 g of a polymer (A), 0.1 g of dicyclopentanyl alcohol which is a compound (B) containing a hydroxy group or an acid group and a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms, The resin composition was mixed with 169.5 g of propylene glycol monomethyl ether which is a solvent (C) to obtain a resin composition of Example 1 in which the concentration of components excluding 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 described below. As a result, the content of the compound (B) was 0.05 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the compound (B).

  In the resin composition of Example 1, the solvent used in producing the polymer (A) was the polymer (A) contained in the polymerization system in which the polymerization reaction was carried out to produce the polymer (A). At the same time, it was used as it was as a raw material. Moreover, as a compound (B), what was brought in from the polymerization system which performed the polymerization reaction in order to manufacture a polymer (A), and what was intentionally added as a raw material of a resin composition were used.

"Content of compound (B)"
The content of the compound (B) means 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 ° C → 20 ° C / min → 250 ° C
Sample: 0.2% by mass acetone solution of resin composition Carrier gas: Helium detector: Hydrogen flame ionization type detector (FID-2010)
Pressure: 120kPa

(Example 2)
A resin composition of Example 2 was obtained in the same manner as Example 1, except that the amount of the compound (B) to be intentionally added as a raw material of the resin composition was changed to 0.5 g. Content of the compound (B) contained in the resin composition of Example 2 was 0.2 mass part with respect to a total of 100 mass parts of a polymer (A) and a compound (B).

(Example 3)
A resin composition of Example 3 was obtained in the same manner as Example 1, except that the amount of the compound (B) to be intentionally added as a raw material of the resin composition was changed to 1.0 g. Content of the compound (B) contained in the resin composition of Example 3 was 0.4 mass part with respect to a total of 100 mass parts of a polymer (A) and a compound (B).

(Example 4)
"Synthesis of Polymer (I)"
101.2 g of propylene glycol monomethyl ether acetate as a solvent was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction pipe, and the mixture was stirred while being purged with nitrogen and heated to 120 ° C. Then, 22.0 g of dicyclopentanyl methacrylate which is a monomer (a1) having a C 10 -C 20 crosslinked cyclic hydrocarbon group, 24. 1 g of methacrylic acid which is an unsaturated acid monomer (a 2), and the like To a monomer mixture consisting of 109.1 g of benzyl methacrylate which is the monomer (a3) of the above, 3.1 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl O) is added The solution was dropped into the flask over 2 hours from a dropping funnel. After completion of the dropwise addition, the mixture was further stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction to obtain a polymer (I) as a polymer (A).

  The acid number and the weight average molecular weight of the obtained polymer (A) were measured in the same manner as in Example 1. As a result, the acid value of the solid content of the polymer (A) was 105 mg KOH / g, and the weight average molecular weight was 17,000.

Next, 158.3 g of a polymer (A), 0.1 g of dicyclopentanyl alcohol which is a compound (B) containing a hydroxy group or an acid group and a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms, 92.3 g of propylene glycol monomethyl ether which is a solvent (C) was mixed to obtain a resin composition of Example 4 in which the concentration of components excluding 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 parts by mass with respect to a total of 100 parts by mass of the polymer (A) and the compound (B).

(Example 5)
A resin composition of Example 5 was obtained in the same manner as Example 4, except that the amount of the compound (B) intentionally added as a raw material of the resin composition was changed to 0.2 g. Content of the compound (B) contained in the resin composition of Example 5 was 0.2 mass part with respect to a total of 100 mass parts of a polymer (A) and a compound (B).

(Example 6)
A resin composition of Example 6 was obtained in the same manner as Example 4, except that the amount of the compound (B) intentionally added as a raw material of the resin composition was changed to 0.5 g. Content of the compound (B) contained in the resin composition of Example 6 was 0.4 mass part with respect to a total of 100 mass parts of a polymer (A) and a compound (B).

(Example 7)
"Synthesis of polymer (II)"
To a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 195.6 g of propylene glycol monomethyl ether acetate as a solvent was added, and the mixture was stirred while being purged with nitrogen and heated to 120 ° C. Next, 22.0 g of dicyclopentanyl methacrylate which is a monomer (a1) having a C 10 -C 20 crosslinked cyclic hydrocarbon group, 49.9 g of methacrylic acid which is an unsaturated acid monomer (a 2), and the like To a monomer mixture consisting of 56.3 g of benzyl methacrylate which is the monomer (a3) of the above, 2.2 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl O) is added The solution was dropped into the flask over 2 hours from a dropping funnel. After completion of the dropwise addition, the mixture was further stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction to obtain a first polymer (polymer (I)).

  Next, the inside of the flask is replaced with 6% oxygen gas, and 43.3 g of glycidyl methacrylate, which is an unsaturated monomer (a4) having a functional group capable of reacting with an acid group, in the flask and triphenylphosphine as a catalyst 0.5 g and 0.1 g of a polymerization inhibitor hydroquinone were added, and an addition reaction was carried out at 120 ° C. for 6 hours to form a polymer (II) as a polymer (A).

  The acid number and the weight average molecular weight of the obtained polymer (A) were measured in the same manner as in Example 1. As a result, the acid value of the solid content of the polymer (A) was 90 mg KOH / g, and the weight average molecular weight was 30,000.

Next, 173.7 g of polymer (A), 0.4 g of dicyclopentanyl alcohol which is a compound (B) containing a hydroxy group or an acid group and a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms, 16.7 g of propylene glycol monomethyl ether which is a solvent (C) was mixed to obtain a resin composition of Example 7 in which the concentration of components excluding the solvent (C) was 45%.
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 with respect to a total of 100 parts by mass of the polymer (A) and the compound (B).

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

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

(Comparative example 1)
"Synthesis of Polymer (I)"
To a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 99.0 g of propylene glycol monomethyl ether acetate as a solvent was added, and the mixture was stirred while being purged with nitrogen and heated to 120 ° C. Next, 0.2 g of dicyclopentanyl methacrylate which is a monomer (a1) having a carbon number of 10 to 20 and a crosslinked cyclic hydrocarbon group, 23.2 g of methacrylic acid which is an unsaturated acid monomer (a2), and the like To a monomer mixture consisting of 128.3 g of benzyl methacrylate which is the monomer (a3) of the above, 3.0 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl O) is added The solution was dropped into the flask over 2 hours from a dropping funnel. After completion of the dropwise addition, the mixture was further stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction to obtain a polymer (I) as a polymer (A).

  The acid number and the weight average molecular weight of the obtained polymer (A) were measured in the same manner as in Example 1. As a result, the acid value of the solid content of the polymer (A) was 105 mg KOH / g, and the weight average molecular weight was 16,800.

Next, the polymer (A) and 90.2 g of propylene glycol monomethyl ether which is a solvent (C) are mixed to obtain a resin composition of Comparative Example 1 in which the concentration of components excluding the solvent (C) is 45%. The
The content of the compound (B) contained in the resin composition of Comparative Example 1 was calculated in the same manner as Example 1. As a result, the content of the compound (B) was 0.0008 parts by mass with respect to a total of 100 parts by mass of the polymer (A) and the compound (B).

(Comparative example 2)
"Synthesis of polymer (II)"
To a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 193.0 g of propylene glycol monomethyl ether acetate as a solvent was added, stirred while replacing with nitrogen, and heated to 120 ° C. Next, 0.2 g of dicyclopentanyl methacrylate which is a monomer (a1) having a carbon number of 10 to 20 and a crosslinked cyclic hydrocarbon group, 47.3 g of methacrylic acid which is an unsaturated acid monomer (a2), and the like To a monomer mixture consisting of 79.0 g of benzyl methacrylate which is the monomer (a3) of the above, 2.2 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl O) is added The solution was dropped into the flask over 2 hours from a dropping funnel. After completion of the dropwise addition, the mixture was further stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction to obtain a first polymer (polymer (I)).

  Next, the inside of the flask is replaced with 6% oxygen gas, and 41.2 g of glycidyl methacrylate, which is an unsaturated monomer (a4) having a functional group capable of reacting with an acid group, in the flask, and triphenylphosphine as a catalyst 0.5 g and 0.1 g of a polymerization inhibitor hydroquinone were added, and an addition reaction was carried out at 120 ° C. for 6 hours to form a polymer (II) as a polymer (A).

  The acid number and the weight average molecular weight of the obtained polymer (A) were measured in the same manner as in Example 1. As a result, the acid value of the solid content of the polymer (A) was 90 mg KOH / g, and the weight average molecular weight was 29,500.

Next, the polymer (A) and 14.6 g of propylene glycol monomethyl ether which is a solvent (C) are mixed to obtain a resin composition of Comparative Example 2 in which the concentration of components excluding the solvent (C) is 45%. The
The content of the compound (B) contained in the resin composition of Comparative Example 2 was calculated in the same manner as Example 1. As a result, the content of the compound (B) was 0.0008 parts by mass with respect to a total of 100 parts by mass of the polymer (A) and the compound (B).

(Comparative example 3)
"Synthesis of polymer (III)"
135.4 g of propylene glycol monomethyl ether acetate as a solvent was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while being purged with nitrogen and heated to 120 ° C. Next, 0.9 g of dicyclopentanyl methacrylate which is a monomer (a1) having a C 10 -C 20 crosslinked cyclic hydrocarbon group and an unsaturated monomer (a 4) having a functional group which reacts with an acid group A monomer mixture consisting of 76.7 g of glycidyl methacrylate and 47.4 g of styrene as the other monomer (a3), 13.8 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, NOF Corporation) And Perbutyl O) were added dropwise from the dropping funnel into the flask over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 120 ° C. for 2 hours for copolymerization reaction to obtain a first polymer (precursor).

  Next, the inside of the flask is replaced with 6% oxygen gas, and in the flask, 38.9 g of acrylic acid which is unsaturated monobasic acid (a5), 0.5 g of triphenylphosphine as a catalyst, and polymerization inhibition 0.1 g of hydroquinone, which is an agent, was added, and the addition reaction was performed at 120 ° C. for 6 hours to form a second polymer.

Next, 53.2 g of tetrahydrophthalic anhydride which is a polybasic acid or its anhydride (a6) is added to the second polymer, and an addition reaction is carried out at 115 ° C. for 3 hours to obtain a polymer (III) as a polymer (A) It was generated.
The acid number and the weight average molecular weight of the obtained polymer (A) were measured in the same manner as in Example 1. As a result, the acid value of the solid content of the polymer (A) was 80 mg KOH / g, and the weight average molecular weight was 7700.

Next, the polymer (A) and 146.8 g of propylene glycol monomethyl ether which is a solvent (C) are mixed to obtain a resin composition of Comparative Example 3 in which the concentration of components excluding the solvent (C) is 45%. The
The content of the compound (B) contained in the resin composition of Comparative Example 3 was calculated in the same manner as Example 1. As a result, the content of the compound (B) was 0.0006 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the compound (B).

(Comparative example 4)
"Synthesis of polymer (III)"
A polymer (A) was prepared in the same manner as in Comparative Example 3 except that dicyclopentanyl methacrylate, which is a monomer (a1) having a carbon number of 10 to 20 and having a crosslinked cyclic hydrocarbon group, was different from that of the manufacturer. Polymer (III) was produced as.
The acid number and the weight average molecular weight of the obtained polymer (A) were measured in the same manner as in Example 1. As a result, the acid value of the solid content of the polymer (A) was 80 mg KOH / g, and the weight average molecular weight was 7800.

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

<Evaluation of resin composition>
The storage stability of each of the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 was evaluated by the methods described below.
Equal parts (10 g) of the resin composition were weighed into a 20 ml glass container and used as a sample. Each of these samples was stored by being allowed to stand for 1 week in a thermostat kept at 40 ° C., and the condition 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 was measured by the same method as the weight average molecular weight (Mw) of the polymer (A) used as a raw material of the resin composition. The results are shown in Table 1.

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

As shown in Table 1, in the resin compositions of Examples 1 to 9, the evaluation of storage stability was ○. On the other hand, in the resin compositions of Comparative Examples 1 to 4, the evaluation of storage stability was x.
It is estimated that this is an effect of the resin compositions of Examples 1 to 9 containing the compound (B) sufficiently.

"Curable resin composition (color resist)"
The color resist (curable resin composition) which contains the component shown in Table 2 in the ratio shown in Table 2 using the sample after the said storage stability evaluation of the resin composition of Examples 1-9 and Comparative Examples 1-4. Was prepared.
In addition, in the compounding quantity of the solvent (C) in Table 2, it is a solvent used when manufacturing a polymer (A), and the quantity of the solvent contained in the resin composition is not contained. The compounding amount of the resin composition in Table 2 includes the amount of the solvent used in producing the polymer (A) and contained in the resin composition.

<Evaluation of color resist>
The developability of the color resists of Examples 1 to 9 and Comparative Examples 1 to 4 was evaluated by the methods described below.
A color resist is spin coated on a 5 cm square glass substrate (alkali free glass substrate) so that the thickness after exposure is 2.5 μm to form a coated film, and the solvent is heated at 90 ° C. for 3 minutes. Volatilized. Next, a photomask of a predetermined pattern was placed at a distance of 100 μm from the coating film, and the coating film was exposed (exposure dose: 150 mJ / cm ² ) through the photomask to photocure the exposed portion.
Next, an aqueous solution containing 0.1% by mass sodium carbonate was sprayed at a temperature of 23 ° C. and a pressure of 0.3 MPa to dissolve and develop an unexposed part. Thereafter, baking was carried out at 210 ° C. for 30 minutes to form a predetermined pattern.

And the residue after alkali development was confirmed by observing the pattern after alkali development using the electron microscope S-3400 by Hitachi High-Technologies Corp., and it evaluated by the criteria shown below. The results are shown in Table 1.
○: no residue on unexposed area ×: residue on unexposed area

As shown in Table 1, the color resists of Examples 1 to 9 were evaluated as ○ for evaluation of developability. On the other hand, in the color resists of Comparative Examples 1 to 4, the evaluation of developability was x.
It is presumed that this is the effect of the color resists of Examples 1 to 9 sufficiently containing the compound (B).

According to the present invention, a resin cured film having excellent developability can be obtained, and a resin composition suitable as a material of a photosensitive resin composition having excellent storage stability can be provided.
The photosensitive resin composition of the present invention provides a cured resin film having excellent developability, and has excellent storage stability. Therefore, the photosensitive resin composition of the present invention can be preferably used as a transparent film, a protective film, an insulating film, an overcoat, a photo spacer, a black matrix, a black column spacer, and a resist for a color filter.

Claims (12)

A polymer (A) having an acid group and a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms,
And a compound (B) containing a hydroxy group or an acid group and a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms,
A resin composition comprising 0.001 to 1.0 parts by mass of the compound (B) with respect to a total of 100 parts by mass of the polymer (A) and the compound (B).   Any one kind selected from the reaction product of an alcohol selected from dicyclopentenyl alcohol, dicyclopentanyl alcohol, isobornyl alcohol, adamantyl alcohol, and the alcohol and a polybasic acid anhydride, as the compound (B) The resin composition according to claim 1 which is the above.   The resin composition according to claim 1 or 2, wherein the polymer (A) has an unsaturated bond.   The resin composition according to any one of claims 1 to 3, further comprising a solvent (C).   The resin composition according to any one of claims 1 to 4, further comprising a reactive diluent (D).   A photosensitive resin composition comprising the resin composition according to any one of claims 1 to 5 and a photopolymerization initiator (E).   The photosensitive resin composition according to claim 6, wherein the photopolymerization initiator (E) is one or both of an acetophenone type and an oxime ester type.   The photosensitive resin composition according to claim 6, 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 cured resin film, which is a cured product of the photosensitive resin composition according to any one of claims 6 to 10.   An image display device comprising the cured resin film according to claim 11.