KR20220010612A - Photosensitive resin composition, cured resin film, and image display element - Google Patents

Abstract

[식 (1) 중, R¹ 은 수소 원자 또는 메틸기를 나타내고, n 은 1 ∼ 10 의 정수이다. 식 (2) 중, R² 는 수소 원자 또는 메틸기를 나타내고, m 은 1 ∼ 10 의 정수이다.](A) a structural unit derived from a polymerizable unsaturated compound having an acid group (a-1), a structural unit represented by the following formula (1) or (2) (a-2), and a structural unit derived from another polymerizable unsaturated compound ( As a copolymer containing a-3), when the total of all structural units is 100 mol%, 20 mol% to 80 mol% of the structural unit (a-2) is included, the weight average molecular weight is 1000 to 50000, and a copolymer having a molecular weight distribution (Mw/Mn) of 1.5 to 3.0;
(B) a solvent containing at least one selected from the group consisting of primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms;
(C) a reactive diluent;
(D) A photoinitiator is included, The photosensitive resin composition characterized by the above-mentioned.

[In Formula (1), R<^1> represents a hydrogen atom or a methyl group, and n is an integer of 1-10. In formula (2), R ² represents a hydrogen atom or a methyl group, and m is an integer of 1 to 10.]

Description

Photosensitive resin composition, cured resin film, and image display element

The present invention relates to a photosensitive resin composition, a cured resin film, and an image display element.

In recent years, with the spread of a liquid crystal display, research on the color filter used as a structural member of a liquid crystal display, the overcoat layer formed on a color filter, an interlayer insulating film, etc. is made|formed actively.

For example, the overcoat layer and the interlayer insulating film require high surface hardness due to their properties, and alkali developability is also required when manufactured by a photolithography process. As a material which has such a performance, in patent document 1, the photosensitive resin composition containing resin (A), a silane coupling agent (B), a polymeric compound (C), a photoinitiator (D), and a solvent (E) This is proposed.

Generally, a liquid crystal display sandwiches a liquid crystal between the color filter board|substrate and TFT (Thin-Film-Transistor) board|substrate manufactured individually, and is manufactured by bonding these board|substrates. Alignment films, such as a polyimide film for orientating a liquid crystal, are formed in the color filter board|substrate. When the alignment film is formed, the color filter substrate is exposed to a solvent with high polarity such as N-methylpyrrolidone (NMP) contained in the polyimide resin. Therefore, solvent resistance (NMP resistance) is required for the color filter substrate. do. Patent Document 2 includes a specific structural unit, a copolymer having a weight average molecular weight of 1000 to 50000 and a molecular weight distribution (Mw/Mn) of 1.5 to 3.0, and a solvent containing a hydroxyl group having 3 to 10 carbon atoms. The photosensitive resin composition for color filters containing the solvent contained, a reactive diluent, a photoinitiator, and a coloring agent is disclosed.

However, in the conventional photosensitive resin composition, there existed a problem that the resin cured film which has the outstanding solvent resistance could not be provided.

Japanese Laid-Open Patent Publication No. 2019-53266 International Publication No. 2018/110097

This invention was made|formed in order to solve the above problems, and provides the resin cured film which has high hardness and the outstanding solvent resistance, and aims at providing the photosensitive resin composition with favorable developability.

Moreover, this invention aims at providing the resin cured film which has high hardness and the outstanding solvent resistance, and the image display element provided with the same.

The present invention includes the following aspects.

[1] (A) a structural unit derived from a polymerizable unsaturated compound having an acid group (a-1), a structural unit (a-2) represented by the following formula (1) or (2), and other polymerizable unsaturated compounds derived from As a copolymer containing a structural unit (a-3), when the sum total of all structural units is 100 mol%, 20 mol% - 80 mol% of structural units (a-2) are included, and a weight average molecular weight is 1000- 50000 and a copolymer having a molecular weight distribution (Mw/Mn) of 1.5 to 3.0;

(B) a solvent containing at least one selected from the group consisting of primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms;

(C) a reactive diluent;

(D) A photoinitiator is included, The photosensitive resin composition characterized by the above-mentioned.

[Formula 1]

[Formula 2]

[In Formula (1), R<^1> represents a hydrogen atom or a methyl group, and n is an integer of 1-10. In formula (2), R ² represents a hydrogen atom or a methyl group, and m is an integer of 1 to 10.]

[2] The acid group of the structural unit (a-1) is a carboxy group, the copolymer (A) contains 10 mol% to 50 mol% of the structural unit (a-1), and the copolymer (A) The photosensitive resin composition according to [1], wherein an acid value of 20 KOHmg/g to 300 KOHmg/g.

[3] The photosensitive resin composition according to [1] or [2], wherein the (B) solvent contains a primary alcohol having 3 to 10 carbon atoms.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the structural unit (a-3) is a structural unit derived from a polymerizable unsaturated compound having a ring structure.

[5] The structural unit (a-3) is at least one selected from the group consisting of styrene, styrene derivatives, vinyltoluene, aromatic group-containing (meth)acrylates and cyclic hydrocarbon group-containing (meth)acrylates The photosensitive resin composition according to any one of [1] to [4], which is a structural unit derived from a polymerizable unsaturated compound.

[6] The structural unit (a-3) consists of styrene, vinyltoluene, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate and dicyclopentanyl (meth) acrylate The photosensitive resin composition in any one of [1]-[5] which is a structural unit derived from the at least 1 sort(s) of polymerizable unsaturated compound chosen from the group.

[7] The photosensitive resin composition according to any one of [1] to [6], containing 1 mol% to 70 mol% of the structural unit (a-3).

[8] When the total of the components excluding the solvent (B) is 100 parts by mass, the content of the copolymer (A) is 5 parts by mass to 85 parts by mass, and the content of the reaction diluent (C) is 5 parts by mass to The photosensitive resin composition in any one of [1]-[7] whose content of 85 mass parts and said (D) photoinitiator is 0.1 mass part - 30 mass parts.

[9] The photosensitive resin composition according to any one of [1] to [8], further comprising (E) a colorant.

[10] A cured resin film, which is a cured product of the photosensitive resin composition according to any one of [1] to [9].

[11] An image display element comprising the cured resin film according to [10].

ADVANTAGE OF THE INVENTION According to this invention, the resin cured film which has high hardness and the outstanding solvent resistance can be provided, and the photosensitive resin composition with favorable developability can be provided. Moreover, according to this invention, the cured resin film which has high hardness and the outstanding solvent resistance, and the image display element provided with this can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. However, this invention is not limited to embodiment shown below.

<Photosensitive resin composition>

The photosensitive resin composition of this embodiment contains (A) copolymer, (B) solvent, (C) reactive diluent, and (D) photoinitiator. The photosensitive resin composition of this embodiment further contains (E) a coloring agent as needed. The photosensitive resin composition of this embodiment is polymerization-hardened by light irradiation, and forms a resin cured film.

[(A) copolymer]

The copolymer (A) in the present embodiment has a structural unit (a-1) derived from a polymerizable unsaturated compound having an acid group (hereinafter, also simply referred to as “structural unit (a-1)”), and the following formula ( A structural unit (a-2) (hereinafter also simply referred to as “structural unit (a-2)”) represented by 1) or (2) and a structural unit (a-3) derived from another polymerizable unsaturated compound (hereinafter, It is also simply referred to as "structural unit (a-3)").

[Formula 3]

[Formula 4]

In formula (1), R<^1> represents a hydrogen atom or a methyl group, and n is an integer of 1-10. In formula (2), R<^2> represents a hydrogen atom or a methyl group, and m is an integer of 1-10.

(A-1) The polymerizable unsaturated compound which has an acidic radical used as the raw material of a structural unit (a-1) will not be specifically limited if it is a monomer which has an acidic radical and an ethylenically unsaturated group. (A-1) Although the acid group which a compound has is not specifically limited, A carboxy group, a phosphoric acid group (-OP(=O)(OH) ₂ ), a sulfonic acid group (-S(=O) ₂ OH), etc. are preferable. From a developable viewpoint, it is especially preferable that an acidic radical is a carboxy group.

(A-1) Specific examples of the compound include, for example, (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acryloyloxyethylsuccinic acid, and 2-acryloyloxyethylphthalic acid. , 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate, etc. are mentioned. Among these, (meth)acrylic acid is preferable from a viewpoint of the reactivity at the time of manufacturing easiness of an acquisition and (A) copolymer. In addition, in this specification, "(meth)acrylic acid" means at least 1 type selected from methacrylic acid and acrylic acid, "(meth)acrylate" is at least 1 selected from methacrylate and acrylate A species is meant, and "(meth)acryloyl" means at least 1 type selected from methacryloyl and acryloyl.

The compound (A-2) used as a raw material of the structural unit (a-2) is a compound represented by the following formula (3) or (4).

[Formula 5]

In formula (3), R<^1> represents a hydrogen atom or a methyl group, and n is an integer of 1-10. R ¹ is preferably a methyl group. It is preferable that it is an integer of 2-6, and, as for n, it is more preferable that it is 3.

[Formula 6]

In formula (4), R<^2> represents a hydrogen atom or a methyl group, and m is an integer of 1-10. R ² is preferably a methyl group. It is preferable that it is an integer of 2-6, and, as for m, it is more preferable that it is 3.

As a specific example of the said (A-2) compound, [(meth)acryloyloxy]methyltriethoxysilane, [(meth)acryloyloxy]ethyltriethoxysilane, [(meth)acryloyl oxide Si]propyltriethoxysilane, [(meth)acryloyloxy]octyltriethoxysilane, [(meth)acryloyloxy]propylmethyldiethoxysilane, [(meth)acryloyloxy]ethylmethyldie Toxysilane, [(meth)acryloyloxy] nonylmethyl diethoxysilane, etc. are mentioned. Among these, 3-[(meth)acryloyloxy]propyltriethoxysilane and 3-[(meth)acryloyloxy]propylmethyldiethoxysilane are preferable from a viewpoint of availability.

(A) When a copolymer contains a structural unit (a-2), the resin cured film which has desired hardness and solvent resistance is obtained. Moreover, there are few changes with time, and the stable (A) copolymer can be obtained, and storage stability at the time of setting it as the photosensitive resin composition is also favorable.

(A-3) Another polymerizable unsaturated compound used as a raw material of the structural unit (a-3) is a polymerizable unsaturated compound other than the (A-1) compound and (A-2) compound, and an acid group and an alkoxysilyl group It is a polymerizable unsaturated compound copolymerizable with (A-1) compound and (A-2) compound without having.

(A-3) As a specific example of another polymerizable unsaturated compound, For example, styrene; α-, o-, m-, p-alkyl, nitro, cyano, and amide derivatives of styrene; vinyltoluene; aromatic group-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, triphenylmethyl (meth)acrylate, naphthalene (meth)acrylate, and anthracene (meth)acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) Cyclic hydrocarbon group-containing (meth)acrylates, such as an acrylate;

Alkyl (meth)acrylates, such as methyl (meth)acrylate, n-propyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; isocyanato group-containing (meth)acrylates such as 2-isocyanatoethyl (meth)acrylate and 3-isocyanatopropyl (meth)acrylate; Blocked isocyanato group containing (meth)acrylate which made the isocyanato group of the said isocyanato group containing (meth)acrylate block using the blocking agent; (meth)acrylic acid amides such as (meth)acrylic acid amide and (meth)acrylic acid N,N-diisopropylamide; Cumyl (meth) acrylate, 3-(N,N-dimethylamino) propyl (meth) acrylate, glycerol mono (meth) acrylate, butanetriol mono (meth) acrylate, glycidyl (meth) acrylic (meth)late, 3,4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, and N,N-dimethylaminoethyl (meth)acrylate ) acrylic acid esters;

dienes such as butadiene; norbornene, norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^{7 , 10]} dodeca-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6] deca-8-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, penta-cyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13] -4-penta-deca-yen and unsaturated cyclic hydrocarbon compounds; vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinylpyridine, vinyl acetate, and vinyltoluene; unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconic acid; Unsaturated polybasic acid anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, etc. are mentioned.

Among these, it is preferable from a viewpoint of the hardness of a cured resin film that (A-3) another polymerizable unsaturated compound is a polymerizable unsaturated compound which has a ring structure. The ring structure is an aromatic ring and a saturated alicyclic structure. The number of ring structures is preferably 1 or 2. It is preferable that carbon number of a saturated alicyclic structure is 5-8. Specifically, polymerizable unsaturated compounds having a ring structure such as styrene, styrene derivatives, vinyltoluene, aromatic group-containing (meth)acrylates, cyclic hydrocarbon group-containing (meth)acrylates, and unsaturated cyclic hydrocarbon compounds are preferable. , styrene, a styrene derivative, vinyltoluene, at least one selected from the group consisting of aromatic group-containing (meth)acrylates and cyclic hydrocarbon group-containing (meth)acrylates is more preferable. From the viewpoint of hardness and solvent resistance of the cured resin film, and storage stability as a photosensitive resin composition, (A-3) other polymerizable unsaturated compounds include styrene, vinyltoluene, phenyl (meth) acrylate, benzyl (meth) acrylate, It is most preferable that it is at least 1 sort(s) selected from the group which consists of cyclohexyl (meth)acrylate and dicyclopentanyl (meth)acrylate.

These (A-3) compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

The proportion of the structural unit (a-2) is 20 mol% to 80 mol%, preferably 20 mol% to 70 mol%, when the total of all structural units of the copolymer (A) is 100 mol% , more preferably 25 mol% to 50 mol%. When the ratio of the structural unit (a-2) is less than 20 mol%, the desired hardness and solvent resistance of the cured resin film cannot be obtained. On the other hand, when the ratio of a structural unit (a-2) is more than 80 mol%, the ratio of a structural unit (a-1) runs short, favorable developability is not acquired, and the storage stability of the photosensitive resin composition is inferior.

The proportion of the structural unit (a-1) is preferably 10 mol% to 50 mol%, and preferably 20 mol% to 40 mol%, when the total of all structural units of the copolymer (A) is 100 mol%. It is more preferable, and it is most preferable that it is 25 mol% - 35 mol%. When the ratio of the structural unit (a-1) is within the above range, good developability is obtained. Moreover, when the ratio of the structural unit (a-3) makes the sum total of all the structural units of (A) copolymer 100 mol%, it is preferable that they are 1 mol% - 70 mol%, and it is 10 mol% - 60 mol% % is more preferable, and it is most preferable that they are 25 mol% to 50 mol%. If the ratio of a structural unit (a-3) is the said range, favorable developability, the hardness of a cured resin film, and solvent resistance are acquired.

(A) The weight average molecular weights (Mw) of a copolymer are 1000-50000, It is preferable that it is 2000-30000, It is more preferable that it is 3000-15000. (A) The solvent resistance of a cured resin film worsens that the weight average molecular weight (Mw) of a copolymer is less than 1000, or the exposure part residual film rate after image development falls. On the other hand, when the weight average molecular weight (Mw) of (A) copolymer is more than 50000, image development time becomes too long, and practicality loses. The value of the weight average molecular weight (Mw) of the copolymer (A) in the present embodiment is measured under the following conditions using gel permeation chromatography (GPC), and is calculated in terms of polystyrene.

Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.)

Column temperature: 40℃

Sample: (A) tetrahydrofuran solution with a copolymer content of 0.2 mass%

Developing solvent: tetrahydrofuran

Detector: Differential Refractometer (Product name: Shodex (registered trademark) RI-71S, manufactured by Showa Denko Co., Ltd.)

Flow rate: 1 ml/min

The molecular weight distribution (Mw/Mn) of the (A) copolymer in this embodiment is 1.5-3.0, it is preferable that it is 1.5-2.5, It is more preferable that it is 1.5-2.0. (A) If the molecular weight distribution (Mw / Mn) of the copolymer is less than 1.5, optimization of the target numerical range such as the weight average molecular weight (Mw) and acid value, (A) reaction conditions for preparing the copolymer, etc. It has to be set by pinpoint, so it is not realistic from the balance between the effort of examination and the effect obtained. On the other hand, when the molecular weight distribution (Mw/Mn) of (A) copolymer is more than 3.0, developability will generate|occur|produce. Molecular weight distribution (Mw/Mn) is measured from the chromatogram of the said GPC measurement.

Although the acid value of (A) copolymer in this embodiment is not specifically limited, It is preferable that they are 20KOHmg/g - 300KOHmg/g, It is more preferable that they are 40KOHmg/g - 200KOHmg/g, 60 Most preferably, it is KOHmg/g to 150 KOHmg/g. (A) More favorable developability is obtained as the acid value of a copolymer is 20 KOHmg/g or more. On the other hand, when the acid value of (A) copolymer is 300 KOHmg/g or less, an exposed part (photocured part) does not melt|dissolve with respect to alkaline developing solution.

In addition, (A) the acid value of the copolymer is a value measured using a mixture indicator of bromothymol blue and phenol red according to JIS K6901 5.3, and is used to neutralize the acidic component contained in (A) 1 g of the copolymer. It means the number of mg of potassium hydroxide required for

Although the unsaturated group equivalent is not specifically limited when (A) copolymer in this embodiment has an unsaturated group, It is preferable that they are 100 g/mol - 4000 g/mol, and 200 g/mol - 3000 g/ It is more preferable that it is mol. (A) When the unsaturated group equivalent of the copolymer is 100 g/mol or more, it is effective for further improving thermal decomposition resistance and thermal yellowing resistance. On the other hand, when the unsaturated group equivalent of (A) copolymer is 4000 g/mol or less, it is effective in raising a sensitivity more.

Although the silyl group equivalent of (A) copolymer in this embodiment is not specifically limited, It is preferable that they are 300 g/mol - 1000 g/mol, It is more preferable that they are 350 g/mol - 900 g/mol , most preferably from 400 g/mol to 800 g/mol. (A) It is effective in improving the storage stability of the photosensitive resin composition more that the silyl group equivalent of a copolymer is 300 g/mol or more. On the other hand, when the silyl group equivalent of (A) copolymer is 1000 g/mol or less, it is effective in improving the hardness and solvent resistance of a cured resin film more.

In addition, (A) the silyl group equivalent (g / mol) of the copolymer is (A) the mass average molecular weight of the copolymer divided by the average number of silyl groups per molecule (A) of the copolymer (A) of the copolymer It is molecular weight, and it is set as the calculated value computed based on the input amount of the compound (A-2) mentioned later.

In the above-mentioned (A) copolymer, in the presence of a solvent, a monomer mixture comprising the compound (A-1), the compound (A-2), and the compound (A-3) is subjected to a radical polymerization method known in the art. It can be prepared by copolymerizing according to For example, after dissolving the compound (A-1), the compound (A-2), and the compound (A-3) in the solvent (B) to prepare a solution, a polymerization initiator is added to the solution, and 50°C to 130°C What is necessary is just to make it react at degreeC for 1 hour - 20 hours. (A) The number of repetitions of each compound in the copolymer and the order in which each compound is bonded are not particularly limited. In addition, after preparing a copolymer not containing any of the structural unit (a-1), the structural unit (a-2), and the structural unit (a-3), the insufficient structural unit is introduced into the copolymer by a modification reaction. and (A) copolymer containing structural unit (a-1), structural unit (a-2), and structural unit (a-3) may be prepared.

(A) The compounding ratio of the monomer for manufacturing a copolymer can be prescribed|regulated for the same reason as having prescribed|regulated the content rate of the said structural unit (a-1) - (a-3). That is, the compounding ratio of (A-2) compound is 20 mol% - 80 mol%, when the sum total of (A-1) - (A-3) compound is 100 mol%, 25 mol% - 70 mol% % is preferable, and it is more preferable that they are 30 mol% - 50 mol%. (A-1) It is preferable that the compounding ratio of a compound is 10 mol% - 50 mol%, It is more preferable that they are 15 mol% - 45 mol%, It is most preferable that they are 20 mol% - 40 mol%. (A-3) It is preferable that the compounding ratio of a compound is 1 mol% - 70 mol%, It is more preferable that they are 15 mol% - 60 mol%, It is most preferable that they are 30 mol% - 50 mol%.

(A) The solvent used when manufacturing a copolymer will not be specifically limited if it is a solvent inactive to a polymerization reaction. It is preferable to use the same solvent as the solvent contained in the photosensitive resin composition to be described later, since there is no need to separate and remove the solvent for the polymerization reaction. In addition, by using at least one solvent selected from the group consisting of primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms, (A) the weight average molecular weight of the copolymer ( While controlling Mw) and molecular weight distribution (Mw/Mn) to a predetermined range, the photosensitive resin composition which has desired storage stability can be obtained easily. When the copolymer (A) is prepared using a solvent containing no primary alcohol and secondary alcohol having 3 to 10 carbon atoms, gelation occurs or the weight average molecular weight (Mw) of the copolymer obtained and Molecular weight distribution (Mw/Mn) does not become in the predetermined range, and the storage stability of the photosensitive resin composition may fall. It is preferable to use the solvent which has a C3-C10 primary alcohol or C3-C10 secondary alcohol as a main component from a viewpoint of the storage stability of the photosensitive resin composition, C3-C10 It is more preferable to use the solvent which has the primary alcohol of 10 as a main component.

Specific examples of the primary alcohol having 3 to 10 carbon atoms and the secondary alcohol having 3 to 10 carbon atoms include monomono such as propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, dodecyl alcohol, and benzyl alcohol. Alcohols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl (poly)alkylene glycol monoalkyl ethers, such as ether and 3-methoxy-1- butanol, etc. are mentioned. Among these, (poly) alkylene glycol monoalkyl ethers are preferable from a viewpoint of the stability at the time of manufacturing easiness of availability and (A) copolymer. These alcohols may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, although various isomers are contained in said alcohol, the isomer corresponding to a tertiary alcohol is not included. For example, 2-propyl alcohol is contained in propyl alcohol other than 1-propyl alcohol.

(A) Other solvents may be contained in the solvent used when manufacturing a copolymer. Examples of the other solvent include tertiary alcohols such as tert-butyl alcohol and diacetone alcohol; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; 2-hydroxymethyl propionate, 2-hydroxypropionate ethyl, 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate ethyl, 3-methoxymethyl propionate, 3-methoxyethyl propionate; 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl ethoxy acetate, ethyl hydroxy acetate, 2-hydroxy-3-methyl butyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl- 3-Methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-propionic acid esters such as butyl, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; Carboxylic acid amides, such as N-methylpyrrolidone, N,N- dimethylformamide, and N,N- dimethylacetamide, etc. are mentioned. Among these, a (poly) alkylene glycol monoalkyl ether acetate type solvent, such as a propylene glycol monomethyl ether acetate from a stability viewpoint at the time of manufacturing (A) copolymer, is preferable.

(A) content of at least 1 sort(s) selected from the group which consists of a C3-C10 primary alcohol and a C3-C10 secondary alcohol in the solvent used when manufacturing a copolymer, It is preferable that they are 10 mass % - 100 mass %, and it is more preferable that they are 20 mass % - 100 mass %. When the content of at least one selected from the group consisting of primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms is within the above range, (A) the weight average molecular weight of the copolymer ( Mw) and molecular weight distribution (Mw/Mn) are easy to control in predetermined ranges, and storage stability of the photosensitive resin composition can be improved more.

(A) Although the quantity of the solvent used when manufacturing a copolymer is not specifically limited, When the sum total of the input amount of (A-1) compound, (A-2) compound, and (A-3) compound is 100 mass parts, , It is preferable that they are 30 mass parts - 1000 mass parts, and it is more preferable that they are 50 mass parts - 800 mass parts. By making the usage-amount of a solvent into 30 mass parts or more, an abnormal polymerization reaction can be prevented and a polymerization reaction can be performed stably, and coloring and gelatinization of (A) copolymer can also be prevented. Moreover, by making the usage-amount of a solvent into 1000 mass parts or less, the fall of the molecular weight of (A) copolymer by chain transfer action can be suppressed, and the viscosity of (A) copolymer can be controlled in an appropriate range.

(A) Although it does not specifically limit as a polymerization initiator which can be used when manufacturing a copolymer, For example, 2,2'- azobis (isobutyronitrile), 2,2'- azobis (2, 4-dimethylvaleronitrile), 2,2'-azobis(isobutyric acid)dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc. are mentioned. These polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.

(A) Although the quantity of the polymerization initiator used when manufacturing a copolymer is not specifically limited, The sum total of the input amount of (A-1) compound, (A-2) compound, and (A-3) compound was 100 mass parts. At the time, it is preferable that they are 0.1 mass part - 20 mass parts, and it is more preferable that they are 0.5 mass part - 16 mass parts.

It is preferable that the compounding quantity of the (A) copolymer in the photosensitive resin composition of this embodiment is 5 mass parts - 85 mass parts, when the total of components excluding the (B) solvent in the said photosensitive resin composition is 100 mass parts, , It is more preferable that they are 15 mass parts - 75 mass parts, and it is most preferable that they are 20 mass parts - 65 mass parts. (A) Sclerosis|hardenability of the photosensitive resin composition becomes more suitable that the compounding quantity of a copolymer is in the said range.

[(B) Solvent]

As the solvent (B) blended in the photosensitive resin composition of the present embodiment, the solvent used in (copolymerization reaction) for producing the copolymer (A) described above can be used as it is, and the solvent exemplified above can be further added. may be Moreover, when adding another component, the solvent coexisting there may be sufficient.

When the compounding quantity of the (B) solvent in the photosensitive resin composition of this embodiment makes the total of components excluding (B) solvent in the said photosensitive resin composition 100 mass parts, it is preferable that they are 30 mass parts - 1000 mass parts, It is more preferable that they are 50 mass parts - 800 mass parts, and it is most preferable that they are 100 mass parts - 700 mass parts. (B) The viscosity of the photosensitive resin composition becomes more suitable that the compounding quantity of a solvent is in the said range.

[(C) Reactive Diluent]

The (C) reactive diluent blended in the photosensitive resin composition of the present embodiment is not particularly limited as long as it is a compound containing an ethylenically unsaturated double bond, but selected from the group consisting of a vinyl group and a (meth)acryloyloxy group It is preferable to include at least 1 type. (C) Specific examples of the reactive diluent include aromatic vinyls such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate, and diallylbenzenephosphonate. monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate ( meth)acrylate monomer; Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane polyfunctional (meth)acrylates such as tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate meth)acrylates; triallyl cyanurate etc. are mentioned. Among these, polyfunctional (meth)acrylates having a plurality of (meth)acryloyl groups are particularly preferable. These (C) reactive diluents may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that the compounding quantity of (C) reactive diluent in the photosensitive resin composition of this embodiment is 5 mass parts - 85 mass parts, when the total of components excluding (B) solvent in the said photosensitive resin composition is 100 mass parts, , It is more preferable that they are 15 mass parts - 75 mass parts, and it is most preferable that they are 20 mass parts - 65 mass parts. (C) The viscosity and photocurability of the photosensitive resin composition become more suitable that the compounding quantity of a reactive diluent is in the said range.

[(D) Photoinitiator]

Although it does not specifically limit as (D) photoinitiator mix|blended with the photosensitive resin composition of this embodiment, For example, Benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and its alkyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; alkylphenones such as 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthone such as 2,4-dimethyl thioxanthone, 2,4-diisopropyl thioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3′,4,4′-tetrakis(t-butyldioxycarbonyl)benzophenone ; 1,2-Octanedione,1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole oxime esters such as -3-yl], 1-(o-acetyloxime); 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; xanthone etc. are mentioned. These (D) photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

When the compounding quantity of the (D) photoinitiator in the photosensitive resin composition of this embodiment makes the total of the component except the (B) solvent in the said photosensitive resin composition 100 mass parts, it is preferable that they are 0.1 mass part - 30 mass parts And, it is more preferable that they are 0.5 mass part - 20 mass parts, and it is most preferable that they are 1 mass part - 15 mass parts. (D) The photocurability of the photosensitive resin composition becomes more suitable that the compounding quantity of a photoinitiator is in the said range.

[(E) Colorant]

The photosensitive resin composition of this embodiment may contain the (E) coloring agent as needed. (E) As a coloring agent, a well-known dye and pigment can be used. (E) When using dye as a coloring agent, compared with the case where a pigment is used, the coloring pattern with a high brightness|luminance can be obtained, and favorable alkali developability is shown.

As the dye, (B) from the viewpoint of solubility in a solvent or alkali developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., an acid dye having an acid group such as a carboxyl group, a salt of an acid dye with a nitrogen compound, It is preferable to use the sulfonamide form of an acid dye, etc. As such a dye, For example, 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, 112, 113, 120, 129, 147; acid chrome violet K ; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95 ; acid 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, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; 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 and derivatives thereof, and the like. Among these, the acid dye of an azo type, a xanthene type, an anthraquinone type, or a phthalocyanine type is preferable. These dyes may be used individually by 1 type depending on the color of the pixel made into the objective, and may be used in combination of 2 or more type.

As the pigment, for example, C.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 , 147, 148, 150, 153, 154, 166, 173, 194, 214 yellow pigments; C.I. Orange pigments, such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 ; C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 60; C.I. Violet pigments, such as pigment violet 1, 19, 23, 29, 32, 36, 38; C.I. Green pigments, such as pigment green 7, 36, and 58; C.I. Brown pigments, such as Pigment Brown 23 and 25; C.I. Black pigments, such as pigment black 1 and 7, carbon black, a titanium black, and iron oxide, etc. are mentioned. These pigments may be used individually by 1 type depending on the color of the pixel made into the objective, and may be used in combination of 2 or more type. Moreover, you may use dye and a pigment together.

It is preferable that the compounding quantity of (E) coloring agent in the photosensitive resin composition of this embodiment is 5 mass parts - 75 mass parts, when the sum total of components excluding (B) solvent in the said photosensitive resin composition is 100 mass parts, It is more preferable that they are 5 mass parts - 65 mass parts, and it is most preferable that they are 10 mass parts - 55 mass parts.

(E) When using a pigment as a coloring agent, you may mix|blend a well-known dispersing agent with the photosensitive resin composition from a viewpoint of improving the dispersibility of a pigment. As a dispersing agent, it is preferable to use the polymer dispersing agent excellent in dispersion stability over time. Examples of the polymer dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene glycol diester-based dispersant, a sorbitan aliphatic ester-based dispersant, and an aliphatic modified ester-based dispersant. have. As such a polymer dispersing agent, EFKA (manufactured by EFKA Corporation), Disperbyk (manufactured by Bikchemi Corporation), Dispalon (manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (manufactured by Zeneca Corporation) are commercially available under trade names. You can use what you have.

The compounding quantity of the dispersing agent in the photosensitive resin composition containing a coloring agent is suitably adjusted with types, such as a pigment.

In addition to said component, in addition to said component, in order to provide predetermined|prescribed characteristic, you may mix|blend well-known additives, such as a well-known leveling agent and a thermal polymerization inhibitor, with the photosensitive resin composition of this embodiment. The compounding quantity of these additives in the photosensitive resin composition will not be specifically limited if it is a range which does not impair the effect of this invention.

The photosensitive resin composition of this embodiment may be prepared by mixing said component using a well-known mixing apparatus, or after preparing the composition containing the (A) copolymer and (B) solvent first, namely, (A-1) compound, (A-2) compound, and (A-3) a monomer mixture composed of compound is copolymerized in the presence of (B) a solvent, (C) a reactive diluent, (D) a photopolymerization initiator and You may prepare by adding and mixing the (E) coloring agent of an arbitrary component. In the latter preparation method, you may further add (B) solvent after copolymerization as needed.

Since the photosensitive resin composition of this embodiment has alkali developability, it can develop by using aqueous alkali solution. In particular, the photosensitive resin composition of this embodiment can provide the pattern excellent in solvent resistance while being excellent in a sensitivity and developability. Therefore, the photosensitive resin composition of this embodiment is used suitably as a resist used in order to manufacture the color filter and its overcoat, and an interlayer insulating film incorporated in an organic electroluminescent display device, a liquid crystal display device, and a solid-state image sensor.

<Cured resin film>

The cured resin film of this embodiment is formed by apply|coating the above-mentioned photosensitive resin composition, making it photocuring, and baking. When forming a pattern by the photolithographic method, after apply|coating the above-mentioned photosensitive resin composition to a base material and forming a coating film, the coating film is exposed through the photomask of a predetermined|prescribed pattern, and an exposure part is photocured. And after developing an unexposed part with aqueous alkali solution, the resin cured film which has a predetermined|prescribed pattern can be formed by baking.

Although it does not specifically limit as a coating method of the photosensitive resin composition, The screen printing method, the roll coat method, the curtain coat method, the spray coat method, the spin coat method, the slit coat method, etc. are used.

After apply|coating the photosensitive resin composition and forming a coating film, you may volatilize the (B) solvent by heating a coating film using heating means, such as a circulation oven, an infrared heater, and a hotplate, as needed. Heating conditions are not specifically limited, According to the composition of the photosensitive resin composition, it is set suitably. For example, what is necessary is just to heat a coating film at the temperature of 50 degreeC - 120 degreeC for 30 second - 30 minutes.

Although it does not specifically limit as a light source used for exposure of the coating film which consists of a photosensitive resin composition, For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp etc. are used. Moreover, exposure amount is not specifically limited, either, It sets suitably according to the composition of the photosensitive resin composition.

Although it does not specifically limit as aqueous alkali solution used for image development, For example, Aqueous solutions, such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide; Aqueous solutions of amine compounds, such as ethylamine, diethylamine, and dimethylethanolamine; Aqueous solutions of quaternary ammonium salts, such as tetramethylammonium hydroxide; 3-Methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N -P-phenylenediamine compounds such as -β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfate, hydrochloride, or p-toluenesulfonate salts of aqueous solution is used. Among these, it is preferable to use the aqueous solution of a p-phenylenediamine type compound. In addition, you may add an antifoamer and surfactant to these aqueous alkali solutions as needed. Moreover, it is preferable to wash with water and to dry after image development by said aqueous alkali solution.

The conditions of baking are not specifically limited, What is necessary is just to heat-process according to the composition of the photosensitive resin composition. For example, what is necessary is just to heat at the temperature of 130 degreeC - 250 degreeC for 10 minutes - 60 minutes.

When the (E) colorant is blended with the photosensitive resin composition to form a cured resin film such as a black matrix or color filter, the desired coloring pattern (pixel) is sequentially obtained by repeating the steps of application, exposure, development and baking for each color. can be formed

[Image display element]

The image display element of this embodiment is equipped with the resin cured film mentioned above. Although it will not specifically limit as an image display element of this embodiment if the resin cured film mentioned above is provided, For example, a liquid crystal display element, organic electroluminescent display element, etc. are mentioned. Since the image display element of this embodiment is equipped with the resin cured film mentioned above, it has high hardness and the outstanding solvent resistance.

Example

Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to the following Example.

In addition, in Examples and Comparative Examples, the silyl group equivalent is the molecular weight of the copolymer (A) divided by the average number of silyl groups per molecule, and is a calculated value calculated based on the amount of (A-2) compound charged .

(A) The synthesis example of a copolymer is shown below.

[Synthesis Example 1]

750.0 g of 3-methoxy-1-butanol was put into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, stirred while replacing with nitrogen gas, and the temperature was raised to 88°C.

Next, a monomer mixture comprising 33.3 g (0.39 mol) of methacrylic acid, 149.7 g (0.52 mol) of 3-methacryloyloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Industries, Ltd.) and 40.3 g (0.39 mol) of styrene. 26.8 g of 2,2'-azobis(isobutyric acid) dimethyl (polymerization initiator) was added dropwise from the dropping funnel to the flask over 2 hours.

After completion of the dropwise addition, the mixture was stirred at 88°C for 5 hours to carry out a copolymerization reaction, and sample 1 (weight average molecular weight (Mw): 4500, number average molecular weight (Mn): 2700, molecular weight distribution (Mw/Mn): 1.7, acid value: 87 KOHmg/g, silyl group equivalent: 480 g/mol) was obtained.

[Synthesis Examples 2 to 17, Comparative Synthesis Examples 1 to 7]

Except using the raw material of Tables 1-3, it carried out similarly to Synthesis Example 1, performed a copolymerization reaction, and obtained Samples 2-24. Tables 1-3 show the weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw/Mn), acid value (KOHmg/g) and silyl group equivalent (g/mol) of the obtained sample. Moreover, the mol% of (A-1) compound - (A-3) compound used for preparing (A) copolymer is shown to Tables 4-6.

<(A) evaluation of copolymer>

(1) storage stability

Using the obtained samples 1-24, the following method evaluated storage stability.

The sample was weighed and put into a 20 ml glass container at a time of 10 g to make a sample, and the viscosity was measured. In addition, in this specification, the viscosity means the value measured at 25 degreeC using the E-type viscometer (RE-80, Toki Industrial Co., Ltd. make, rotor type: standard cone 1°34' x R24, rotor code: 1) do. Then, the glass container was sealed with a lid, and after leaving these samples to stand still for 1 week in the thermostat kept at 40 degreeC, respectively, and preserve|save, the viscosity was measured again. The thickening rate was calculated|required from following formula (1) using the viscosity before and behind a storage stability test.

Formula (1): thickening rate (%) = (([viscosity after test] - [viscosity before test])/[viscosity before test]) x 100

The criteria for this evaluation are as follows.

○: Less than 20% thickening rate

x: thickening rate 20% or more

The evaluation result of said storage stability is shown to Tables 7-9.

Using the obtained samples 1-24, the photosensitive resin composition was prepared according to the following method.

<Preparation of the photosensitive resin composition>

According to the compounding component and compounding ratio shown in Table 10, the photosensitive resin composition was prepared.

In addition, the compounding quantity of (A) copolymer in Table 10 does not contain the solvent used when synthesize|combining (A) copolymer, The compounding quantity of (B) solvent in Table 10 is (A) public It is the sum of the solvent used when synthesizing the coal and propylene glycol monomethyl ether further blended.

<Evaluation of the photosensitive resin composition>

(1) pencil hardness

After spin-coating the prepared photosensitive resin composition so that the thickness after baking may be set to 2.5 micrometers on a 5 cm horizontal glass substrate (alkali-free glass substrate), a solvent is volatilized by heating at 90 degreeC for 3 minutes, and a glass substrate A coating film was formed on it.

Next, the coating film was exposed to light with a wavelength of 365 nm at an exposure amount of 200 mJ/m 2 , the exposed portion was photocured, and then left in an air atmosphere in a drying machine with a baking temperature of 230° C. for 30 minutes to prepare a cured coating film. . According to JISK5600-5-4, the pencil hardness of the obtained cured coating film was measured using the pencil hardness meter (No.553-M, Yasuda Seki Seisakusho).

The criteria for this evaluation are as follows.

○: pencil hardness 3H or more

×: pencil hardness less than 3H

The evaluation result of said pencil hardness is shown to Tables 7-9.

Using the obtained samples 1-24, the coloring agent containing photosensitive resin composition was prepared according to the following method.

<Preparation of a colorant containing photosensitive resin composition>

According to the compounding component and compounding ratio shown in Table 11, the coloring agent containing photosensitive resin composition using dye (VALIFAST BLUE 2620) was prepared as (E) coloring agent.

In addition, the compounding quantity of (A) copolymer in Table 11 does not contain the solvent used when synthesize|combining (A) copolymer, The compounding quantity of (B) solvent in Table 11 is (A) public It is the sum of the solvent used when synthesizing the coal and propylene glycol monomethyl ether further blended.

<Evaluation of the colorant-containing photosensitive resin composition>

(1) alkali developability

The prepared colorant-containing photosensitive resin composition is spin-coated on a 5 cm wide glass substrate (alkali-free glass substrate) so that the thickness after exposure becomes 2.5 μm, and then heated at 90° C. for 3 minutes to volatilize the solvent, A coating film was formed on the glass substrate.

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 amount: 150 mJ/cm 2 ) through the photomask, and the exposed portion was photocured.

Next, when an unexposed part is dissolved and developed by spraying an aqueous solution containing 0.1 mass % potassium hydroxide at a temperature of 23°C and a pressure of 0.3 MPa, the time required until the pattern starts to be seen, that is, the start of development Time was measured.

The criteria for this evaluation are as follows.

○: Development start time less than 60 seconds

×: Development start time 60 seconds or more

The evaluation result of said alkali developability is shown to Tables 7-9.

(2) Solvent resistance

The prepared colorant-containing photosensitive resin composition is spin-coated on a 5 cm-wide glass substrate (alkali-free glass substrate) so that the thickness after baking becomes 2.5 μm, and then heated at 90° C. for 3 minutes to volatilize the solvent, A coating film was formed on the glass substrate.

Next, the coating film was exposed to light having a wavelength of 365 nm at an exposure amount of 150 mJ/m 2 , the exposed portion was photocured, and then left in an air atmosphere in a drying machine with a baking temperature of 230° C. for 30 minutes to prepare a cured coating film. .

200 mL of N-methyl-2-pyrrolidone was put into a 500-mL glass bottle with a lid, and it left still on 60 degreeC conditions. After immersing the said test piece with a cured coating film in that, it left still for 30 minutes in the state hold|maintained at 60 degreeC.

^{The color change (ΔE*} ab) before and after immersion in N-methyl-2-pyrrolidone of the test piece was measured with a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation).

The criteria for this evaluation are as follows.

○: ΔE ^* ab is less than 3.0

×: ΔE ^* ab is 3.0 or more

The evaluation result of said solvent resistance is shown to Tables 7-9.

From the results of Tables 7 and 8, the copolymer (A) obtained in Synthesis Examples 1 to 17 shows excellent storage stability, and the photosensitive resin composition using the copolymer (A) obtained in Synthesis Examples 1 to 17 has high hardness. The resin cured film which has was provided, and the coloring agent containing photosensitive resin composition using the (A) copolymer obtained by Synthesis Examples 1-17 provided the pattern excellent in alkali developability and solvent resistance (Examples 1-17).

In contrast, (A-2) of Comparative Synthesis Examples 1 and 2 using 3-(methacryloyloxy)propyltrimethoxysilane and 3-(methacryloyloxy)propylmethyldimethoxysilane instead of compound (A-2) A) The copolymer did not have sufficient storage stability (Comparative Examples 1 and 2). The methoxy-type alkoxysilyl group is presumed to be because the reactivity is high compared with the ethoxy-type. Further, the copolymers (A) of Comparative Synthesis Examples 3 and 4 in which a solvent containing at least either a primary alcohol having 3 to 10 carbon atoms or a secondary alcohol was not used did not have sufficient storage stability ( Comparative Examples 3 and 4). A tertiary alcohol solvent and a non-alcoholic solvent have weak solvation with respect to water, and it is guessed because it is because the hydrolysis reaction of an alkoxysilyl group advances easily.

(A-1) Although the coloring photosensitive resin composition using the (A) copolymer of the comparative synthesis example 5 which does not contain a compound had favorable solvent resistance, alkali developability was inadequate (comparative example 5). (A-2) The photosensitive resin composition using the copolymer (A) of Comparative Synthesis Example 6 having a compound content of 10 mol% has insufficient hardness and color photosensitivity using the copolymer (A) of Comparative Synthesis Example 6 Although the resin composition had favorable alkali developability, solvent resistance was inadequate (Comparative Example 6). Moreover, although the solvent resistance of the photosensitive resin composition using the (A) copolymer of the comparative synthesis example 7 whose content rate of (A-2) compound is 90 mol% was favorable, alkali developability was inadequate.

Industrial Applicability

ADVANTAGE OF THE INVENTION According to this invention, while providing the resin cured film which has high hardness and the outstanding solvent resistance, developability is favorable, and the photosensitive resin composition excellent also in storage stability is provided. Moreover, the cured resin film which has high hardness and the outstanding solvent resistance, and the image display element provided with this are provided. The photosensitive resin composition 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 the resist for color filters.

Claims (11)

(A) a structural unit derived from a polymerizable unsaturated compound having an acid group (a-1), a structural unit represented by the following formula (1) or (2) (a-2), and a structural unit derived from another polymerizable unsaturated compound ( As a copolymer containing a-3), when the total of all structural units is 100 mol%, 20 mol% to 80 mol% of the structural unit (a-2) is included, the weight average molecular weight is 1000 to 50000, and a copolymer having a molecular weight distribution (Mw/Mn) of 1.5 to 3.0;
(B) a solvent containing at least one selected from the group consisting of primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms;
(C) a reactive diluent;
(D) A photoinitiator is included, The photosensitive resin composition characterized by the above-mentioned.

[In Formula (1), R<^1> represents a hydrogen atom or a methyl group, and n is an integer of 1-10. In formula (2), R ² represents a hydrogen atom or a methyl group, and m is an integer of 1 to 10.] The method of claim 1,
The acid group of the structural unit (a-1) is a carboxy group, the copolymer (A) contains 10 mol% to 50 mol% of the structural unit (a-1), and the acid value of the copolymer (A) The photosensitive resin composition of 20 KOHmg/g - 300 KOHmg/g. 3. The method according to claim 1 or 2,
The photosensitive resin composition in which the said (B) solvent contains a C3-C10 primary alcohol. 4. The method according to any one of claims 1 to 3,
The photosensitive resin composition in which the said structural unit (a-3) is a structural unit derived from the polymerizable unsaturated compound which has a ring structure. 5. The method according to any one of claims 1 to 4,
The structural unit (a-3) is at least one polymerizable unsaturated selected from the group consisting of styrene, styrene derivatives, vinyltoluene, aromatic group-containing (meth)acrylates and cyclic hydrocarbon group-containing (meth)acrylates The photosensitive resin composition which is a structural unit derived from a compound. 6. The method according to any one of claims 1 to 5,
The structural unit (a-3) is selected from the group consisting of styrene, vinyltoluene, phenyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate and dicyclopentanyl (meth)acrylate The photosensitive resin composition which is a structural unit derived from at least 1 type of polymerizable unsaturated compound used as 7. The method according to any one of claims 1 to 6,
The photosensitive resin composition containing 1 mol% - 70 mol% of the said structural unit (a-3). 8. The method according to any one of claims 1 to 7,
When the total of the components excluding the (B) solvent is 100 parts by mass, the content of the copolymer (A) is 5 parts by mass to 85 parts by mass, and the content of the reaction diluent (C) is 5 parts by mass to 85 parts by mass The photosensitive resin composition whose content of said (D) photoinitiator is 0.1 mass part - 30 mass parts. 9. The method according to any one of claims 1 to 8,
(E) A photosensitive resin composition further comprising a colorant. It is hardened|cured material of the photosensitive resin composition in any one of Claims 1-9, The resin cured film characterized by the above-mentioned. The cured resin film of Claim 10 is provided, The image display element characterized by the above-mentioned.