KR20130120394A - Photosensitive resin composition - Google Patents

Abstract

As a photosensitive resin composition containing (A) binder resin, (B) polymeric compound, (C) polymerization initiator and starting adjuvant, and (D) solvent, the weight average molecular weights of (A) binder resin are 8,000 or more and 100,000 or less, (C) The polymerization initiator and the starting aid contain at least an oxime compound, an acylphosphine oxide compound, and a thioxanthone compound, and the solvent (D) has a solubility parameter of 8.0 to 9.1 (cal / cm 3) ^1/2. It contains 70 mass% or more and 99 mass% or ^{less of a} phosphorus solvent, and contains 1 mass% or more and 30 mass% or less of the solvent whose solubility parameter is 9.2-11.0 (cal / cm <3>) ^1/2 .

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a photosensitive resin composition.

JP2010-140042-A includes a resin, a photopolymerizable compound, a colorant, and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [trade name: Irgacure (registered trademark) OXE And a photosensitive resin composition using propylene glycol monoethyl ether acetate as a solvent.

In the conventional photosensitive resin composition, the hardness and tackiness of the pattern obtained from this composition may not always be satisfied.

MEANS TO SOLVE THE PROBLEM As a result of examining in order to solve said subject, the present inventors discovered that the composition containing some kind of solvent gives the pattern which has satisfactory hardness and adhesiveness.

That is, this invention provides the following [1]-[11].

[1] A photosensitive resin composition comprising (A) binder resin, (B) polymerizable compound, (C) polymerization initiator and starting aid, and (D) solvent, wherein (A) weight average molecular weight of binder resin is 8,000 or more It is 100,000 or less, (C) The polymerization initiator and the start adjuvant contain at least an oxime type compound, an acylphosphine oxide type compound, and a thioxanthone type compound, and (D) solvent has a solubility parameter of 8.0-9.1 (cal / cm <3>). ) A solvent containing ^{1/2 or more} of solvents having a solubility parameter of 9.2 to 11.0 (cal / cm 3) ^{1/2 and} containing at least 1% by mass to 30% by mass of the solvent do.

[2] The photosensitive resin composition as described in [1], in which the solid acid value of the (A) binder resin is 80 or more and 200 or less.

[3] When the ratio of (A) binder resin and (B) polymerizable compound is expressed as (A) binder resin / (B) polymerizable compound on a mass basis, it is 50/50 or more and 80/20 or less [1] or The photosensitive resin composition as described in [2].

[4] The photosensitive resin composition according to any one of [1] to [3], further containing (E) a colorant.

[5] The photosensitive resin composition according to any one of [1] to [4], further comprising (F) a leveling agent, wherein the amount of the leveling agent is 0.001% by mass or more and 0.3% by mass or less.

[6] A patterned coating film formed of the photosensitive resin composition according to any one of [1] to [5].

[7] a step of applying the photosensitive resin composition according to any one of [1] to [5] on a support and removing a solvent to form a coating film,

A method of producing a patterned coating film comprising the step of exposing the coating film after masking and removing an unexposed portion of the coating film with a developing solution.

[8] a step of applying the photosensitive resin composition according to any one of [1] to [5] on a support, removing a solvent to form a coating film, and

The manufacturing method of the patterned coating film which consists only of a process of exposing after exposing the said coating film and removing the unexposed part of the said coating film with a developing solution.

[9] a step of applying the photosensitive resin composition according to any one of [1] to [5] on a support and removing a solvent to form a coating film;

Exposing said coating film after masking and removing the unexposed part of said coating film with a developing solution, and

The manufacturing method of the patterned coating film containing the process of maintaining the coating film which removed the unexposed part with the developing solution at the temperature of 23 degreeC or more and 200 degrees C or less.

[10] A color filter comprising the patterned coating film described in [6].

[11] A color filter comprising a patterned coating film obtained by the production method according to any one of [7] to [9].

According to this invention, it becomes possible to provide the photosensitive resin composition which gives the pattern which has satisfactory hardness and adhesiveness.

The photosensitive resin composition of this invention contains (A) binder resin, (B) polymeric compound, (C) polymerization initiator and starting adjuvant, and (D) solvent.

The photosensitive resin composition of this invention contains (A) binder resin. (A) Binder resin has an unsaturated compound (b) (following) which has an oxiranyl group in addition polymer (a) (Hereinafter, it may be called "(a)") which has a structural unit derived from unsaturated carboxylic acid. And binder resin (A1) (Hereinafter, it may be called "resin (A1).") Which made it react with "(b)".

In addition, resin (binder resin) in the pigment dispersion liquid of the (E) coloring agent mentioned later shall not be contained in (A) binder resin.

As (a), for example, a monomer (a2) having an unsaturated carboxylic acid (a1) (hereinafter sometimes referred to as "(a1)") and an unsaturated bond capable of addition polymerization with (a1) and (b) (hereinafter, The addition polymer obtained by addition-polymerizing "(a2)" may be mentioned.

Specific examples of (a1) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinyl benzoic acid, m-vinyl benzoic acid and p-vinyl benzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate, mono [2- ] Esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as α- (hydroxymethyl) acrylic acid.

Of these, acrylic acid, methacrylic acid and the like are preferably used in terms of copolymerization reactivity or alkali solubility.

In the present specification, the term "(meth) acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Quot ;, &quot; (meth) acryloyl &quot;, and &quot; (meth) acrylate &quot;

As (a2), (meth), such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, for example Acrylic acid alkyl esters;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (referred to in the art as dicyclo (Meth) acrylate cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

Aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclo-unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Especially as (a2), the compound (a2-1) which has at least 1 sort (s) of skeleton chosen from the group which consists of a tricyclodecane skeleton and a tricyclodecene skeleton, and ethylenically unsaturated bond [hereinafter "(a2-1)" May be referred to]. (a2-1), it is possible to suppress film reduction of the pattern due to development.

Here, the "tricyclodecane skeleton" and the "tricyclodecene skeleton" in this specification mean the following structures (each having a coupling | bonding number in arbitrary places), respectively.

As (a2-1), specifically, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) Acrylate is mentioned. These may be used alone or in combination of two or more.

As (b), for example, a monomer obtained by epoxidizing a chain olefin and a monomer (b-1) having an ethylenically unsaturated bond (hereinafter may be referred to as "(b-1)"), a structure obtained by epoxidizing cycloalkene and ethylene The monomer (b-2) which has a sex unsaturated bond (Hereinafter, it may be called "(b-2)") is mentioned. (b-1) is preferable from the viewpoint of reactivity.

Specifically as (b-1), glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycy Dyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis ( Glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxy Methyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) Styrene, the compound described in JPH07-248625-A, etc. are mentioned.

Examples of (b-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane [eg, ceoxide 2000; Daicel Kagaku Kogyo Co., Ltd.], 3, 4- epoxycyclohexyl methyl acrylate [for example, cyclomer A400; Daicel Kagaku Kogyo Co., Ltd.], 3,4-epoxycyclohexylmethyl methacrylate [for example, cyclomer M100; Daicel Kagaku Kogyo Co., Ltd.], the compound represented by general formula (I), the compound represented by general formula (II), etc. are mentioned.

[Formula (I) and Formula (II), R <^1> and R <^2> represents a hydrogen atom or a C1-C4 alkyl group independently of each other, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

X ¹ and X ² independently represent a single bond, -R ³ -, -R ³ -O-, -R ³ -S- or -R ³ -NH-.

R <^3> represents a C1-C6 alkanediyl group.

* Represents the number of bonds with O.]

Binder resin (A1) can be manufactured through a two-step process, for example. In this case, for example, a method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Publishing Co., Ltd., 1st edition, 1st edition, published on Mar. 1, 1972), and Japanese Patent Laid-Open Publication No. 2001-89533 Can be produced by referring to the method described in the publication.

In manufacture of binder resin (A1), the addition polymer (a) of (a1) and (a2) is obtained first as a 1st step. Specifically, a method of stirring, heating, and warming in an atmosphere of deoxygenation is exemplified by injecting a predetermined amount of (a1) and (a2), a polymerization initiator, a solvent, and the like into a reaction vessel and replacing oxygen with nitrogen. . The polymerization initiator, solvent and the like to be used herein are not particularly limited, and any of those commonly used in the relevant fields can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (such as benzoyl peroxide) The solvent may be any one which dissolves the respective monomers, and a solvent to be described later may be used as a solvent of the colored photosensitive resin composition.

In addition, the obtained addition polymer may use the solution after reaction as it is, may be used as a concentrated or diluted solution, and may use what extracted as solid (powder) by methods, such as reprecipitation.

It is preferable that the ratio of the structural unit derived from (a1) and (a2) exists in the following ranges with respect to the total mole number of all the structural units which comprise an addition polymer.

a structural unit derived from the structural unit (a1); 5-50 mol% (more preferably 10-45 mol%)

a structural unit derived from the structural unit (a2); 50-95 mol% (more preferably 55-90 mol%)

Next, as a 2nd step, a part of carboxylic acid of (a1) derived from the obtained addition polymer is made to react with (b). Since reactivity is high and it is hard to remain unreacted (b), (b-1) is preferable.

Specifically, the atmosphere in the flask is subsequently replaced with nitrogen to air after 5 to 80 mol% of the mole number of (a1), and a reaction catalyst such as tris (dimethylaminomethyl) phenol and the like ( 0.001-5 mass% with respect to the total amount of a1), (b) and (a2) and 0.001-5 mass% with respect to the total amount of (a1), (b) and (a2) and polymerization inhibitor (for example, hydroquinone etc.). To the flask, the reaction is usually carried out at 60 ℃ to 130 ℃ for 1 to 10 hours to obtain a resin (A1). In addition, as in the case of the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production facility or polymerization.

In this case, the number of moles of (b) is preferably 10 to 75 mol%, more preferably 15 to 70 mol% with respect to the number of moles of (a1). When the number of moles of (b) is within this range, balance between storage stability, solvent resistance and heat resistance tends to be improved.

As a specific example of binder resin (A1), resin which made glycidyl (meth) acrylate react with the copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / benzyl (meth) acrylate Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of, resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate, (meth) acrylic acid Resin which glycidyl (meth) acrylate was made to react with the copolymer of / styrene, resin which glycidyl (meth) acrylate was made to react with the copolymer of (meth) acrylic acid / methyl (meth) acrylate, (meth) acrylic acid Glycidyl (meth) acrylate was reacted with a resin of glycidyl (meth) acrylate in a copolymer of / N-cyclohexylmaleimide and a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate. Suzy;

(Meth) acrylate is reacted with a copolymer of crotonic acid / cyclohexyl (meth) acrylate and a resin obtained by reacting a copolymer of crotonic acid / benzyl (meth) acrylate with glycidyl (Meth) acrylate on a copolymer of crotonic acid / styrene, a resin obtained by reacting a copolymer of crotonic acid / methyl crotonate with glycidyl (meth) acrylate, a crotonic acid / A resin obtained by reacting a copolymer of N-cyclohexylmaleimide with glycidyl (meth) acrylate;

(Meth) acrylate is added to a copolymer of maleic acid / dicyclopentanyl (meth) acrylate and a copolymer of maleic acid / benzyl (meth) acrylate with glycidyl (Meth) acrylate is reacted with a copolymer of maleic acid / cyclohexyl (meth) acrylate, glycidyl (meth) acrylate is allowed to react with a copolymer of maleic acid / styrene A resin obtained by reacting a copolymer of maleic acid / methyl maleic acid with glycidyl (meth) acrylate, or a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / N-cyclohexylmaleimide ;

(Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate, a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl A resin obtained by reacting a copolymer of glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate, (Meth) acrylic acid / maleic anhydride / methyl (meth) acrylate is copolymerized with a copolymer of a (meth) acrylic acid / maleic anhydride / styrene copolymer and a glycidyl (meth) (Meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide; a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide;

(Meth) acrylic acid / dicyclopentanyl (meth) acrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / Epoxy cyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting (meth) acrylic acid / Styrene is reacted with 3,4-epoxycyclohexylmethyl methacrylate, and a copolymer of (meth) acrylic acid / methyl (meth) acrylate is reacted with 3,4-epoxycyclohexylmethyl methacrylate Resin, a resin obtained by reacting a copolymer of (meth) acrylic acid / N-cyclohexylmaleimide with 3,4-epoxycyclohexylmethyl methacrylate;

Epoxycyclohexylmethyl methacrylate on a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate and a copolymer of crotonic acid / benzyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, Cyclohexylmethyl methacrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of crotonic acid / cyclohexyl (meth) acrylate, and a copolymer of crotonic acid / styrene with 3, 4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of crotonic acid / methyl crotonate and a resin obtained by reacting crotonic acid / N-cyclohexylmaleimide A resin obtained by reacting a copolymer with 3,4-epoxycyclohexylmethyl methacrylate;

A resin obtained by reacting a copolymer of maleic acid / dicyclopentanyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, and a copolymer of maleic acid / benzyl (meth) acrylate with 3,4-epoxycyclo Maleic acid / cyclohexyl (meth) acrylate is reacted with 3,4-epoxycyclohexylmethyl methacrylate, a copolymer obtained by reacting maleic acid / cyclohexyl (meth) acrylate with 3,4- 4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of maleic acid / methyl maleic acid with 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting maleic acid / N-cyclohexylmaleimide A resin obtained by reacting a copolymer with 3,4-epoxycyclohexylmethyl methacrylate;

(Meth) acrylic acid / maleic anhydride / benzyl (meth) acrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (Meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate was added to a copolymer of 3,4-epoxycyclohexylmethyl methacrylate and 3,4-epoxycyclohexylmethyl methacrylate (Meth) acrylic acid / maleic anhydride / (meth) acrylic acid / maleic anhydride / styrene, a resin obtained by reacting a (meth) acrylic acid / maleic anhydride / (Meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide was added to a copolymer of 3,4-epoxycyclohexylmethyl methacrylate and 3,4-epoxycyclohexylmethyl methacrylate Krill There may be mentioned resins such as by reacting the site.

Moreover, as binder resin (A1), it is more preferable that it is resin obtained by making (b) react with the addition polymer obtained by copolymerizing (a2) other than (a1), (a2-1), and (a2-1). . When binder resin (A1) is the said structure, the pattern obtained tends to be excellent in adhesiveness and solvent resistance with a board | substrate.

When an addition polymer (a) consists of (a2) other than (a1), (a2-1), and (a2-1), it originates in (a2) other than (a2-1) and (a2-1) 10: 90-40: 60 are preferable, as for the ratio of a structural unit, 10: 90-40: 60 are more preferable, and 10: 90-30: 70 are still more preferable.

As resin obtained by making (b) react with the addition polymer obtained by copolymerizing (a2) other than (a1) and (a2-1) and (a2-1), (meth) acrylic acid / dicyclopentanyl ( Of a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of meth) acrylate / benzyl (meth) acrylate and (meth) acrylic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate Resin obtained by reacting glycidyl (meth) acrylate with a copolymer, resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / styrene, (meth Resin by which glycidyl (meth) acrylate was made to react the copolymer of acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate, (meth) acrylic acid / dicyclopentanyl (meth) acrylate / N- Written in copolymers of cyclohexylmaleimide Resin to which lycidyl (meth) acrylate is reacted;

A resin obtained by reacting a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with glycidyl (meth) acrylate, a crotonic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (Meth) acrylate is reacted with a copolymer of a crotonic acid / dicyclopentanyl (meth) acrylate / styrene copolymer and glycidyl (meth) (Meth) acrylate / dicyclopentanyl (meth) acrylate / methyl crotonate, a resin obtained by reacting glycidyl (meth) A resin obtained by reacting glycidyl (meth) acrylate with a copolymer of methyl methacrylate and methyl methacrylate;

A resin obtained by reacting a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with glycidyl (meth) acrylate, maleic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (Meth) acrylate is reacted with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / styrene and a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / dicyclopentanyl , A resin obtained by reacting a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / methyl maleic acid with glycidyl (meth) acrylate, a resin obtained by reacting maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmale A resin obtained by reacting glycidyl (meth) acrylate with a copolymer of methyl methacrylate and methyl methacrylate;

(Meth) acrylic acid / maleic anhydride / maleic anhydride / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, a resin obtained by reacting a copolymer of (meth) acrylic acid / maleic anhydride / (Meth) acrylate / maleic anhydride / dicyclopentanyl (meth) acrylate, a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate and cyclohexyl (meth) (Meth) acrylate in a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate, a resin obtained by reacting glycidyl (Meth) acrylate, a resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide;

A resin obtained by reacting a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting (meth) acrylic acid / dicyclopentanil (Meth) acrylate / cyclohexyl (meth) acrylate, a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / dicyclopentanyl (Meth) acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate was added to a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate A resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide;

(Meth) acrylate / dicyclopentanyl (meth) acrylate / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate, a resin obtained by reacting 3,4- A copolymer obtained by reacting a copolymer of cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / styrene and 3,4-epoxycyclo A resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonate and a resin obtained by reacting crotonic acid / dicyclohexylmethyl methacrylate, A resin obtained by reacting a copolymer of fentanyl (meth) acrylate / N-cyclohexylmaleimide with 3,4-epoxycyclohexylmethyl methacrylate;

A resin obtained by reacting a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, a resin obtained by reacting maleic acid / dicyclopentanyl (meth) Cyclohexyl (meth) acrylate is reacted with 3,4-epoxycyclohexylmethyl methacrylate, and a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / styrene and 3,4-epoxycyclohexylmethyl methacrylate is added to a copolymer of maleic acid / Maleic acid / dicyclopentanyl (meth) acrylate / maleic acid methyl ester, maleic acid / dicyclopentanyl (meth) acrylate / maleic acid methyl ester and maleic acid / dicyclohexylmethyl methacrylate; a resin obtained by reacting 3,4- A resin obtained by reacting a copolymer of fentanyl (meth) acrylate / N-cyclohexylmaleimide with 3,4-epoxycyclohexylmethyl methacrylate;

A resin obtained by reacting a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, a (meth) acrylic acid / maleic (Meth) acrylic acid / maleic anhydride / dicyclopentyl (meth) acrylate / dicyclohexyl (meth) acrylate / cyclohexyl (meth) (Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / (meth) acrylate / styrene copolymer, and a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate (Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide copolymerized with 3,4-epoxycyclohexylmethyl methacrylate A resin or the like can be given by reacting a 3,4-epoxycyclohexylmethyl methacrylate.

You may use these binder resins (A1) individually or in combination of 2 or more types.

The weight average molecular weight (Mw) of polystyrene conversion of binder resin (A1) is 8,000-100,000, Preferably it is 10,000-50,000. If the weight average molecular weight of resin (B1) exists in the said range, applicability | paintability and adhesiveness tend to become favorable, and a film | membrane decrease does not occur easily at the time of image development, and also removeability of a non-pixel part at the time of image development. This tends to be good.

The acid value of binder resin (A1) becomes like this. Preferably it is 50-200 mg-KOH / g, More preferably, it is 60-190 mg-KOH / g, More preferably, it is 80-180 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the binder resin (A1), and can be obtained by titration using an aqueous potassium hydroxide solution.

It is preferable that the binder resin (A) contained in the photosensitive resin composition of this invention consists only of binder resin (A1) mentioned above, However, if it is a grade which does not impair the effect of this invention, it can contain other resin. Examples of such resins include epoxy resins, acrylic resins, urethane resins, polyester resins, polyimide resins, polyolefin resins, novolac resins, polyamine resins, and the like.

When binder resin (A) contains resin other than binder resin (A1), as for content of binder resin (A1), 1-80 mass% is preferable with respect to binder resin (A), and 1-50 mass% is More preferred.

The photosensitive resin composition of this invention contains the (B) polymeric compound. The polymerizable compound (B) is not particularly limited as long as it is a compound capable of initiating polymerization by an active radical, an acid or the like generated from the polymerization initiator (C) by the action of light or heat. (B) As a polymeric compound, the compound etc. which have a polymerizable carbon-carbon unsaturated bond are mentioned, Preferably a monofunctional monomer, a bifunctional monomer, or a trifunctional or more than polyfunctional monomer is used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrrolidone Etc. can be mentioned.

Moreover, as a specific example of a bifunctional monomer, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate And bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of the trifunctional or higher polyfunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipenta Reaction product of erythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride, reactant of dipentaerythritol penta (meth) acrylate and acid anhydride, V # 1000, V made by Osaka Yuki Kagaku Co., Ltd. Urethane acrylates such as # 802, STAR-501, UA-306H, UA-306T, UA-306I manufactured by Kyoeisha Kagaku Co., Ltd., and New Frontier R-1150 manufactured by Daiichi Kyo Seiyaku Co., Ltd. . Among them, a bifunctional monomer and a multifunctional monomer having three or more functional groups are preferably used.

Moreover, it is also possible to add the following polymeric compound.

(B) A polymeric compound can be used individually or in combination of 2 or more types.

(B) 1-50 mass% is preferable with respect to solid content of the photosensitive resin composition, and, as for content of a polymeric compound, 5-30 mass% is more preferable. In addition, when the ratio of (A) binder resin and (B) polymeric compound is represented as (A) binder resin / (B) polymeric compound on a mass basis, it is preferable that they are 50/50 or more and 80/20 or less.

When the ratio of (A) binder resin and (B) polymeric compound exists in said range, since adhesiveness is suppressed and there exists a tendency which can obtain the color filter without color unevenness, it is preferable.

The photosensitive resin composition of this invention contains the (C) polymerization initiator and an initiator.

(C) As a polymerization initiator and an initiator, active radical generator, an acid generator, a polymerization promoter, a sensitizer, etc. are mentioned. Active radical generators generate active radicals by the action of light or heat. (C) The polymerization initiator and the start aid include an oxime compound, an acylphosphine oxide compound, and a thioxanthone compound.

As said oxime type compound, the compound which has a partial structure represented by general formula (C-1) is mentioned. In the following formulae, * represents a bond number.

Examples of such oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1- On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl- 2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Compounds, such as 3-cyclopentyl propane-1-one- 2-imine, and commercial items, such as Irgacure (trademark) OXE01, OXE02 (above, BASF Corporation), N-1919 (ADEKA Corporation), etc. Can be mentioned. Especially, Irgacure (trademark) OXE01 (made by BASF Corporation) is preferable.

As said acylphosphine oxide type compound, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6- trimethyl benzoyl)-phenyl phosphine oxide, etc. are mentioned. You may use commercial items, such as Lucirin (trademark) TPO (made by BASF Corporation) and Irgacure (registered trademark) 819 (made by BASF Corporation).

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- Propoxy thioxanthone etc. are mentioned. Especially, 2, 4- diethyl thioxanthone is preferable.

Moreover, as long as it does not impair the effect of this invention, the polymerization initiator or polymerization initiator normally used in this field can be used together further, As said polymerization initiator or polymerization initiator, it is acetophenone type compound and a biimidazole type, for example. A compound, a triazine type compound, a benzoin type compound, a benzophenone type compound, an anthracene type compound, an amine type compound, a thiazolin type compound, an alkoxy anthracene type compound, a carboxylic acid type compound, etc. are mentioned.

Examples of the acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 2-hydroxy-1- [4- (2-hydroxy Methoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone , 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholi Nophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1 -(4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-dimethylbenzyl ) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-di Methylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2- Bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -buta Non, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4- Morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2- Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4 -Methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morph Polynophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo-4 -Methoxy Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one Oligomers and the like.

As said biimidazole type compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2, 3- dichlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole (see eg JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis (2-chlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2 ' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5 '-Tetra (trialkoxyphenyl) biimidazole (see, eg, JPS48-38403-B, JPS62-174204-A, etc.), wherein the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group An imidazole compound (for example, see JPH07-10913-A etc.) etc., Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenylbiimi Dazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

As said triazine type compound, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra (tert- Butyl peroxycarbonyl) benzophenone, 2, 4, 6-trimethyl benzophenone, etc. are mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. have.

As said amine type compound, for example, triethanolamine, methyl diethanolamine, triisopropanolamine, 4-dimethylamino benzoic acid methyl, 4-dimethylamino benzoic acid ethyl, 4-dimethylamino benzoic acid isoamyl, 2-dimethylaminoethyl benzoate, 4 -Dimethylamino benzoic acid 2-ethylhexyl, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Myhiler ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable.

As a thiazolin type compound, the compound etc. which are represented by general formula (III-1)-general formula (III-3) are mentioned.

As said alkoxy anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene etc. are mentioned, for example. Can be.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Diphenylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

In addition, a commercially available brand name "EAB-F" (made by Hodogaya Kagaku Kogyo Co., Ltd.) etc. is illustrated as a (C) polymerization initiator.

Moreover, the polymerization initiator described in JP2002-544205-A can be used as a polymerization initiator which has group which can cause chain transfer among (C) polymerization initiators.

The polymerization initiator which has the group which can cause said chain transfer can be used also as a structural component (A3) of said copolymer. And the obtained copolymer can be used also as (A) binder resin.

As (C) start adjuvant, the above-mentioned amine type compound, thiazolin type compound, alkoxy anthracene type compound, a carboxylic acid type compound, a commercial brand name "EAB-F", etc. are mentioned, for example.

The content of the polymerization initiator (C) and the initiator is preferably 1 to 20 mass% of the oxime compound, the acylphosphine oxide compound, and the thioxanthone compound, respectively, with respect to the solid content of the photosensitive resin composition. The content of the polymerization initiator (C) and the initiator is preferably in a mass fraction with respect to the total amount of the (A) binder resin and the (B) polymerizable compound, preferably 0.1 to 40 mass%, and more preferably 1 to 30 mass. %to be.

(C) When the total amount of a polymerization initiator and a starting aid is in the said range, the photosensitive resin composition will become high sensitivity, and in the intensity | strength of the pixel part of the color filter formed using said photosensitive resin composition, and the surface of said pixel It is preferable because the smoothness of tends to be good.

It is preferable that the photosensitive resin composition of this invention contains the (E) coloring agent further. Although a pigment and dye are mentioned as such a (E) coloring agent, It is preferable to contain a pigment from a heat resistant and light resistant point.

Examples of the pigments include organic pigments and inorganic pigments, and compounds classified into pigments by the color index (Published by The Society of Dyers and Colourists).

As an organic pigment, specifically, 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 and 214;

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, ;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 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. Pigment black 1, pigment black 7, and the like.

Among them, C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242, 254, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15: 3, 15: 6, and C.I. Pigment Green 7, 36 and 58 are more preferable. You may use these pigments individually or in mixture of 2 or more types.

The pigment may be subjected to a surface treatment using a pigment derivative or a pigment dispersing agent to which a rosin treatment, an acidic group or a basic group is introduced, a graft treatment on a pigment surface with a polymer compound or the like, an atomization treatment using a sulfuric acid atomization method, A cleaning treatment with an organic solvent or water to remove impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. It is preferable that the pigment has a uniform particle size. By containing a pigment dispersant and carrying out a dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

Commercially available surfactants can be used as the pigment dispersant, for example, surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic Etc. can be mentioned. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, and the like. KP [manufactured by Shin-Etsukagaku Kogyo Co., Ltd.], Floren [manufactured by Kyoeisha Kagaku Co., Ltd.], Solsperth [manufactured by Geneka Co., Ltd.], EFKA (manufactured by BASF Corporation), Ajisper (registered trademark) [Manufactured by Ajinomoto Fine Techno Co., Ltd.], Disperbyk (manufactured by BIC Chemi Co., Ltd.) and the like. These can be used individually or in combination of 2 types or more, respectively.

When using a pigment dispersant, the usage-amount is preferably 100 mass% or less with respect to a pigment, More preferably, it is 5-50 mass%. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency for the pigment dispersion liquid of a uniform dispersion state to be obtained.

Content of (E) coloring agent becomes like this. Preferably it is 5-60 mass% with respect to solid content of the photosensitive resin composition, More preferably, it is 5-45 mass%. If content of the (E) coloring agent is the said range, a desired spectral or color density can be obtained.

The solvent (D) in the photosensitive resin composition of the present invention includes a solvent having a solubility parameter of 8.0 to 9.1 (cal / cm 3) ^{1/2 and} a solvent having a solubility parameter of 9.2 to 11.0 (cal / cm 3) ^1/2 . do.

Examples of the solvent having a solubility parameter of 8.0 to 9.1 (cal / cm 3) ^1/2 include ethylene glycol mono i-butyl ether, diethylene glycol mono 2-ethylhexyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol mono n- Butyl ether, tripropylene glycol mono n-propyl ether, tripropylene glycol mono n-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di n-butyl ether, triethylene Glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol mono n-butyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, npropyl acetate, N-propionate, n-butyl propionate, n-pentyl propionate, methyl isobutyl ketone, cyclohexane, Toluene, ethyl acetate, butyl acetate, tetrahydrofuran, carbon tetrachloride, and the like can be mentioned 2-heptanone. Among them, propylene glycol monomethyl ether acetate is preferable from the viewpoint of solubility.

Examples of solvents having a solubility parameter of 9.2 to 11.0 (cal / cm 3) ^1/2 include ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, Ethylene glycol monobenzyl ether, ethylene glycol monoallyl ether, diethylene glycol monomethyl ether, diethylene glycol mono n-butyl ether, diethylene glycol monohexyl ether, diethylene glycol mono 2-ethylhexyl ether, diethylene glycol monobenzyl Ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono n-butyl ether, polyethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n- Butyl ether, propylene glycol mono t-butyl ether, propylene glycol Monophenyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol mono n-butyl ether acetate, propylene glycol diacetate, methyl-3-methoxypropionate, methyl lactate, butyl lactate, cyclohexa Paddy, diacetone alcohol, 1-propanol, 1-butanol, methyl ethyl ketone, dioxane, dichloromethane, chloroform, dimethyl sulfoxide, acetone, dimethyl carbonate, 1,1,2,2-tetrachloroethane and the like. have. Among these, propylene glycol monomethyl ether is preferable from a solubility viewpoint.

The content of the solvent (D) is preferably 70% by mass or more and 99% by mass or less in the solvent having a solubility parameter of 8.0 to 9.1 (cal / cm 3) ^1/2 to the total solvent in the photosensitive resin composition, and the solubility parameter is 9.2. 1 mass% or more and 30 mass% or less of the solvent which is -11.0 (cal / cm <3>) ^1/2 , More preferably, 70 mass% or more and 97 mass of the solvent whose solubility parameter is 8.0-9.1 (cal / cm <3>) ^1/2 It is 3 mass% or more and 30 mass% or less of% or less and the solvent whose solubility parameter is 9.2-11.0 (cal / cm <3>) ^1/2 . When the ratio of the mass% of the solvent is in the above range, solubility and flatness at the time of coating tend to be improved.

The solubility parameter can be determined by the following equation.

Solubility Parameter = (ΔE / V) ^1/2

ΔE: cohesive energy (evaporation enthalpy), V: molar volume

(D) Solvent is used at the time of synthesis | combination of (A) binder resin, and when adjusting as a photosensitive resin composition, 70 mass% or more and 99 mass% or less of the solvent whose solubility parameter is 8.0-9.1 (cal / cm <3>) ^1/2 The solvent having a solubility parameter of 9.2 to 11.0 (cal / cm 3) ^1/2 may be 1 mass% or more and 30 mass% or less.

(D) Content of a solvent becomes like this. Preferably it is 60-95 mass% with respect to the photosensitive resin composition, More preferably, it is 70-90 mass%. In other words, solid content of the photosensitive resin composition becomes like this. Preferably it is 5-40 mass%, More preferably, it is 10-30 mass%. When content of (D) solvent exists in the said range, there exists a tendency for the flatness at the time of application | coating to become favorable.

The photosensitive resin composition of this invention may contain (F) surfactant. As surfactant, a silicone type surfactant, a fluorine type surfactant, the silicone type surfactant which has a fluorine atom, etc. are mentioned, for example. By including surfactant, the flatness at the time of application | coating tends to become favorable.

As silicone type surfactant, surfactant which has a siloxane bond is mentioned. Specifically, doray silicon DC3PA, doray silicon SH7PA, doray silicon DC11PA, doray silicon SH21PA, doray silicon SH28PA, doray silicon SH29PA, doray silicon SH30PA, polyether modified silicone oil SH8400 [brand name: doray silicon Dow Corning Corporation], KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsukagaku Kogyo Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan Corporation).

As a fluorine-type surfactant, surfactant which has a fluorocarbon chain | strand is mentioned. Specifically, fluoride (trademark) FC430, fluoride FC431 (manufactured by Sumitomo 3M Co., Ltd.), megapack (registered trademark) F142D, megapack F171, megapack F172, megapack F173, megapack F177, megapack F183, Megapack R30 (manufactured by DIC Corporation), F-Top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Material Denshi Kasei Co., Ltd.), suffron (registered trademark) ) S381, Supron S382, Supron SC101, Supron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Kogyo Co., Ltd.), and the like.

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain | strand is mentioned. Specifically, Mega Pack (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, Mega Pack F443 (manufactured by DIC Corporation), and the like. Preferably Megapack (trademark) F475 is mentioned.

Surfactant is 0.001 mass% or more and 0.3 mass% or less with respect to the photosensitive resin composition, More preferably, they are 0.002 mass% or more and 0.2 mass% or less, Especially preferably, they are 0.01 mass% or more and 0.1 mass% or less. When the surfactant is contained in this range, the flatness of the coating film can be improved.

The photosensitive resin composition of the present invention may contain various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, and chain transfer agents, if necessary.

The photosensitive resin composition of this invention uses (A) binder resin, (B) polymeric compound, (C) polymerization initiator, and an initiator as needed in presence of (E) coloring agent, (D) solvent, and another component as needed. It is obtained by mixing.

In addition, when mixing a pigment as (E) coloring agent, it is preferable to prepare in the following procedures, for example.

First, the pigment is previously mixed with the solvent (D), and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all part of a pigment dispersant and (A) binder resin as needed. In the obtained pigment dispersion liquid, the remainder of (A) binder resin, the other components used as needed, such as (B) polymeric compound and (C) polymerization initiator, and further the additional solvent as needed, and predetermined density | concentration It can be added so that a photosensitive resin composition can be obtained.

As a coating method to the board | substrate of the photosensitive resin composition of this invention, an extrusion coating method, the direct gravure coating method, the reverse gravure coating method, the CAP (cap) coating method, the die coating method, etc. are mentioned, for example. In addition, even if a coating apparatus such as dip coater, roll coater, bar coater, spin coater, slit & spin coater, slit coater (die coater, curtain float coater, spunless coater) good. Among them, it is preferable to apply by using a slit coater, a spin coater, a roll coater or the like.

As a drying method of the film | membrane apply | coated to the board | substrate, methods, such as heat drying, natural drying, ventilation drying, reduced pressure drying, etc. are mentioned, for example, You may carry out combining several methods.

As drying temperature, 10 degreeC-120 degreeC is preferable, and 25 degreeC-100 degreeC is more preferable. Moreover, as heating time, it is preferable that it is for 10 second-60 minutes, and it is more preferable that it is for 30 second-30 minutes.

It is preferable to perform pressure reduction drying in the temperature range of 20 degreeC-25 degreeC under the pressure of 50-150 Pa.

The film thickness of the coating film after drying is not specifically limited, According to the material, a use, etc. to be used, it can adjust suitably, For example, it is 0.1-20 micrometers, Preferably it is 1-6 micrometers.

The coating film after drying is exposed through the photomask for forming the target pattern. The pattern shape on the photomask at this time is not specifically limited, The pattern shape according to the intended use is used.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, light having a wavelength of less than 350 nm may be cut using a filter that cuts the wavelength region, or light having wavelengths around 436 nm, 408 nm, and 365 nm may be selectively extracted using a band- Or may be taken out. As a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned specifically ,.

It is preferable to use an apparatus such as a mask aligner or a stepper because it is possible to uniformly irradiate the entire exposure surface with a parallel light beam or to precisely align the mask with the substrate.

After exposure, a pattern can be obtained by making a coating film contact a developing solution, dissolving and developing a predetermined part, for example, an unexposed part. Although an organic solvent can also be used as a developing solution, since the exposed part of a coating film does not melt | dissolve easily or swells with a developing solution and can obtain a pattern of a favorable shape, it is preferable to use the aqueous solution of an alkaline compound.

The developing method may be paddle method, dipping method, spray method, or the like. In addition, you may tilt the board | substrate at arbitrary angles at the time of image development.

It is preferable to wash with water after image development.

As said alkaline compound, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, hydrogen carbonate Inorganic alkaline compounds such as potassium, sodium borate, potassium borate and ammonia; Tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, Organic alkaline compounds, such as ethanolamine, are mentioned. Especially, potassium hydroxide, sodium hydrogencarbonate, and tetramethylammonium hydroxide are preferable.

The concentration in the aqueous solution of these inorganic and organic alkaline compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

The aqueous solution of the alkaline compound may contain a surfactant.

As the surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters Nonionic surfactants such as polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester and polyoxyethylene alkylamine;

Anionic surfactants such as sodium lauryl alcohol sulfate ester, sodium oleyl alcohol sulfate ester, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate;

Cationic surfactants such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and the like.

The concentration of the surfactant in the aqueous solution of the alkaline compound is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, particularly preferably 0.1 to 5% by mass.

In this invention, the process of heating and holding after image development can also be skipped. Moreover, if necessary, the process of heating and holding can be put.

In the present invention, the temperature of the step of heating and holding is usually 23 ° C or more and 200 ° C or less, preferably 25 ° C or more and 180 ° C or less, more preferably 25 ° C or more and 160 ° C or less, still more preferably 25 ° C or more and 120 ° C. It is as follows. As time to keep warm, it is 1-300 minutes normally, Preferably it is 1-180 minutes, More preferably, it is 1-60 minutes.

If it is possible to omit the step of keeping warm, the number of steps in the step can be reduced and the manufacturing cost can be lowered. In addition, if the process of heating and holding | maintaining can be skipped, a film board | substrate can be used and a flexible display can be manufactured.

The photosensitive composition of this invention can obtain the favorable pattern, such as a color density, brightness, contrast, a sensitivity, a resolution, heat resistance, and the color filter containing this pattern. In addition, these color filters or patterns are well-known to apparatuses related to colored images such as display devices including these as part of components thereof, for example, known liquid crystal displays, organic EL devices, solid-state imaging devices, and electronic paper. It can be used as an aspect.

Example

<Synthesis of Binder Resin Solution A1>

67 weight part of propylene glycol monomethyl ether acetates and 33 weight part of propylene glycol monomethyl ethers were taken to the flask provided with the stirring apparatus, the dropping funnel, the condenser, the thermometer, and the gas introduction tube, and it heated up at 120 degreeC, stirring while nitrogen-substituting. Next, perbutyl O (tert-butyl peroxy-2-ethylhexanoate, Nihon) was added to a monomer mixture composed of 11 parts by weight of tricyclodecanyl methacrylate, 31 parts by weight of benzyl methacrylate, and 23 parts by weight of methacrylic acid. Yushi Corporation) was added 1 part by weight based on 100 parts by weight of the monomer mixture. This was dripped at the flask over 2 hours using the dropping funnel, and it stirred at 120 degreeC for 2 hours, and obtained the copolymer. Subsequently, the flask was replaced with air substitution, and 10 parts by weight of glycidyl methacrylate, 0.46 part by weight of triphenylphosphine and 0.08 part by weight of methylhydroquinone were added to the solution of the copolymer, and the reaction was continued at 120 ° C. for solid content. When the acid value reaches 150 KOHmg / g, the reaction is terminated, and by adding 75 parts by weight of propylene glycol monomethyl ether acetate and 5 parts by weight of propylene glycol monomethyl ether, an alkali developable binder resin having a nonvolatile content of 30% (Mw: 3 0000) ) Solution A1 was obtained.

<Synthesis of Binder Resin Solution A2>

67 weight part of propylene glycol monomethyl ether acetates and 33 weight part of propylene glycol monomethyl ethers were taken to the flask provided with the stirring apparatus, the dropping funnel, the condenser, the thermometer, and the gas introduction tube, and it heated up at 120 degreeC, stirring while nitrogen-substituting. Next, perbutyl O (tert-butyl peroxy-2-ethylhexanoate, Nihon) was added to a monomer mixture consisting of 10 parts by weight of tricyclodecanyl methacrylate, 34 parts by weight of benzyl methacrylate, and 20 parts by weight of methacrylic acid. Yushi Corporation) was added 1 part by weight based on 100 parts by weight of the monomer mixture. This was dripped at the flask over 2 hours using the dropping funnel, and it stirred at 120 degreeC for 2 hours, and obtained the copolymer. Subsequently, the flask was replaced with air replacement, 10 parts by weight of glycidyl methacrylate, 0.44 parts by weight of triphenylphosphine and 0.08 parts by weight of methylhydroquinone were added to the solution of the copolymer, and the reaction was continued at 120 ° C. for solid content. The reaction was terminated when the acid value reached 130 KOHmg / g, and 74 parts by weight of propylene glycol monomethyl ether acetate and 5 parts by weight of propylene glycol monomethyl ether were added to alkali developable binder resin having a nonvolatile content of 30% (Mw: 30000). Solution A2 was obtained.

<Synthesis of binder resin solution A3> Resin A based on JP2010-140042-A

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen, and then heated to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, monomethacrylate of the tricyclodecane skeleton [FA-513M by Hitachikasei Co., Ltd.] 22.0 g (0.10 mol), and propylene glycol The solution which added 3.6 g of azobisisobutyronitrile to the mixture which consists of 136 g of monomethyl ether acetates was dripped at the flask over 2 hours using the dropping funnel, and stirring was continued at 100 degreeC for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g [0.25 mol of glycidyl methacrylate ((50 mol% of the carboxyl groups of methacrylic acid used in this reaction)]] and 0.9 g of trisdimethylaminomethylphenol And 0.145 g of hydroquinone were charged into a flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a binder resin solution A3 (Mw: 13000) having a solid acid value of 79 mgKOH / g.

<Synthesis of Binder Resin Solution A4>

591 parts of propylene glycol monomethyl ether acetate were introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen. 153 parts of propylene glycol monomethyl ether acetate in the monomer mixture which consists of 17.6 parts of methacrylates, 113.7 parts of glycidyl methacrylates, and 22.0 parts of monomethacrylates (Hitachi Chemical Co., Ltd. FA-513M) of a tricyclodecane skeleton. The solution to which 3.6 parts of azobisisobutyronitrile was added was dripped at the flask over 2 hours using the dropping funnel, and stirring was continued at 100 degreeC for 2 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 68.9 parts of methacrylic acid, 0.9 g of trisdimethylaminomethylphenol, and 0.145 part of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to give a solid acid value of 1 The reaction was terminated when it became mgKOH / g.

Next, 53.3 parts of tetrahydro phthalic anhydride and 0.8 part of triethylamine were added and reacted at 120 ° C for 3 hours and 30 minutes to give a binder resin solution A4 (Mw: 7900) having a solid content of 37.9% and an acid value of 68.6 mgKOH / g (in terms of solid content). Got it.

<Synthesis of Binder Resin Solution A5>

A proper amount of nitrogen was flowed into a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer to obtain a nitrogen atmosphere, and 100 parts by weight of propylene glycol monomethyl ether acetate was added thereto and heated to 85 ° C while stirring. Subsequently, in the flask, 19 parts by weight of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [compound represented by formula (I-1) and represented by formula (II-1) Compound] 171 parts by weight of a solution dissolved in 40 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours using a dropping pump. In addition, the flask which melt | dissolved the solution which melt | dissolved 26 weight part of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 120 weight part of propylene glycol monomethyl ether acetate over the flask over about 5 hours using the other dropping pump. It was dripped inside. After completion of the dropwise addition of the polymerization initiator, the mixture was kept at the same temperature for about 3 hours, and then cooled to room temperature to give a binder resin solution A5 (Mw: 8000) having a solid content of 43.5 wt% and an acid value of 52 mgKOH / g (solid content equivalent). Got.

The measurement of the weight average molecular weight (Mw) of the binder resin solution obtained by the synthesis example was performed on condition of the following using GPC method.

Apparatus: K2479 [manufactured by Shimadzu Seisakusho Corporation]

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 DEG C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 ml / min

Detector: RI

Example 1

[Preparation of photosensitive resin composition 1]

Colorant (E): C.I. Pigment Red 242 15 parts,

Colorant (E): C.I. Pigment Red 177 20 parts,

14 parts of an acrylic pigment dispersant,

10 parts of binder resin solution (A1) (solid content conversion), and

Propylene Glycol Monomethyl Ether Acetate-191 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

280 parts of binder resin solution (A1);

Polymerizable compound (B): glycerol 1,3-diglycerolate diacrylate

40 parts (GDDA; manufactured by Aldrich);

Polymerization initiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-

[Irgacure (R) OXE-01; BASF Japan company] 4.0 parts;

Polymerization initiator (C): bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Irgacure (R) 819; BASF Japan Co., Ltd.] 8.0 parts;

Polymerization initiator (C): Diethyl thioxanthone

4.0 parts of KAYACURE (registered trademark) DETX-S Nihon Kayaku Co., Ltd .;

Solvent (D): 409 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Doore Dow Corning Co., Ltd.] 0.5 parts

To obtain a photosensitive resin composition 1.

The solvent of the obtained photosensitive resin composition was 92.7 mass% of propylene glycol monomethyl ether acetate in all the solvents, and was 7.3 mass% of propylene glycol monomethyl ether. In addition, the ratio of binder resin (A1) and a polymeric compound (B) was 70/30 in conversion of solid content.

Example 2

[Preparation of photosensitive resin composition 2]

Colorant (E): C.I. Pigment Green 58 43 parts,

Colorant (E): C.I. Pigment Yellow 138, part 24,

12 parts of an acrylic pigment dispersant,

26 parts of binder resin solution (A1) (solid content conversion), and

Propylene glycol monomethyl ether acetate 390 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

133 parts of binder resin solution (A1);

Polymerizable compound (B): dipentaerythritol hexaacrylate

44 parts of KAYARAD (registered trademark) DPHA (manufactured by Nihon Kayaku Co., Ltd.);

Polymerization initiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-

[Irgacure (R) OXE-01; BASF Japan Co., Ltd.] 11 parts;

Polymerization initiator (C): bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Irgacure (R) 819; BASF Japan Co., Ltd.] 8.8 parts;

Polymerization initiator (C): Diethyl thioxanthone

11 parts [manufactured by KAYACURE (registered trademark) DETX-S Nihon Kayaku Co., Ltd.);

Solvent (D): 322 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Doore Dow Corning Co., Ltd.] 0.5 parts

To obtain a photosensitive resin composition 2.

The solvent of the obtained photosensitive resin composition was 96.4 mass% of propylene glycol monomethyl ether acetate in the whole solvent, and was 3.6 mass% of propylene glycol monomethyl ether. In addition, the ratio of binder resin (A1) and a polymeric compound (B) was 60/40 in conversion of solid content.

Example 3

[Preparation of photosensitive resin composition 3]

Colorant (E): C.I. Pigment Blue 15: 6 27 parts,

Colorant (E): C.I. 0.5 parts of Pigment Violet 23,

10 parts of an acrylic pigment dispersant,

8.3 parts of binder resin solution (A1) (solid content conversion), and

Propylene glycol monomethyl ether acetate 140 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

248 parts of binder resin solution (A1);

Polymerizable compound (B): dipentaerythritol hexaacrylate

35 parts of KAYARAD® DPHA (manufactured by Nihon Kayaku Co., Ltd.);

Polymerization initiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-

[Irgacure (R) OXE-01; BASF Japan Co., Ltd.] 5.8 parts;

Polymerization initiator (C): bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Irgacure (R) 819; BASF Japan Co., Ltd.] 9.4 parts;

Polymerization initiator (C): Diethyl thioxanthone

4.7 parts [manufactured by KAYACURE® DETX-S Nihon Kayaku Co., Ltd.);

Solvent (D): 507 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Doore Dow Corning Co., Ltd.] 0.5 parts

To obtain a photosensitive resin composition 3.

The solvent of the obtained photosensitive resin composition was 93.7 mass% of propylene glycol monomethyl ether acetate in the total solvent, and 6.3 mass% of propylene glycol monomethyl ether. In addition, the ratio of binder resin (A1) and a polymeric compound (B) was 70/30 in conversion of solid content.

Example 4

[Preparation of photosensitive resin composition 4]

Colorant (E): C.I. Pigment Blue 15: 6 27 parts,

Colorant (E): C.I. 0.5 parts of Pigment Violet 23,

10 parts of an acrylic pigment dispersant,

7.4 parts of binder resin solution (A2) (solid content conversion), and

Propylene glycol monomethyl ether acetate 140 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

209 parts of binder resin solution (A2);

Polymerizable compound (B): dipentaerythritol hexaacrylate

47 parts of KAYARAD® DPHA (manufactured by Nihon Kayaku Co., Ltd.);

Polymerization initiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-

[Irgacure (R) OXE-01; BASF Japan Co., Ltd.] 5.8 parts;

Polymerization initiator (C): bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Irgacure (R) 819; BASF Japan Co., Ltd.] 9.4 parts;

Polymerization initiator (C): Diethyl thioxanthone

4.7 parts [manufactured by KAYACURE® DETX-S Nihon Kayaku Co., Ltd.);

Solvent (D): 530 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Doore Dow Corning Co., Ltd.] 0.5 parts

To obtain a photosensitive resin composition 4.

The solvent of the obtained photosensitive resin composition was 94.7 mass% of propylene glycol monomethyl ether acetate in the total solvent, and 5.3 mass% of propylene glycol monomethyl ether. In addition, the ratio of binder resin (A2) and a polymeric compound (B) was 60/40 in conversion of solid content.

Example 5

[Preparation of photosensitive resin composition 5]

Colorant (E): C.I. Pigment Blue 15:62 Part 27,

Colorant (E): C.I. 0.5 parts of Pigment Violet 23,

10 parts of an acrylic pigment dispersant,

7.4 parts of binder resin solution (A1) (solid content conversion), and

Propylene glycol monomethyl ether acetate 140 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

268 parts of binder resin solution (A1);

Polymerizable compound (B): dipentaerythritol hexaacrylate

29 parts of KAYARAD® DPHA (manufactured by Nihon Kayaku Co., Ltd.);

Polymerization initiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-

[Irgacure (R) OXE-01; BASF Japan Co., Ltd.] 5.8 parts;

Polymerization initiator (C): bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Irgacure (R) 819; BASF Japan Co., Ltd.] 9.4 parts;

Polymerization initiator (C): Diethyl thioxanthone

4.7 parts [manufactured by KAYACURE® DETX-S Nihon Kayaku Co., Ltd.);

Solvent (D): 494 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Doore Dow Corning Co., Ltd.] 0.5 parts

To obtain a photosensitive resin composition 5.

The solvent of the obtained photosensitive resin composition was 93.2 mass% of propylene glycol monomethyl ether acetate in the total solvent, and 6.8 mass% of propylene glycol monomethyl ether. In addition, the ratio of binder resin (A1) and a polymeric compound (B) was 75/25 in conversion of solid content.

Example 6

[Preparation of photosensitive resin composition 6]

Colorant (E): C.I. Pigment Blue 15: 6 27 parts,

Colorant (E): C.I. 0.5 parts of Pigment Violet 23,

10 parts of an acrylic pigment dispersant,

8.3 parts of binder resin solution (A1) (solid content conversion), and

Propylene glycol monomethyl ether acetate 140 parts

A pigment dispersion obtained by mixing the mixture and sufficiently dispersing the pigment using a bead mill;

248 parts of binder resin solution (A1);

Polymerizable compound (B): dipentaerythritol hexaacrylate

35 parts of KAYARAD® DPHA (manufactured by Nihon Kayaku Co., Ltd.);

Polymerization initiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-

[Irgacure (R) OXE-01; BASF Japan Co., Ltd.] 5.8 parts;

Polymerization initiator (C): bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Irgacure (R) 819; BASF Japan Co., Ltd.] 9.4 parts;

Polymerization initiator (C): Diethyl thioxanthone

4.7 parts [manufactured by KAYACURE® DETX-S Nihon Kayaku Co., Ltd.);

Solvent (D): 190 parts of propylene glycol monomethyl ethers

Solvent (D): 317 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Doore Dow Corning Co., Ltd.] 0.5 parts

To obtain a photosensitive resin composition 6.

The solvent of the obtained photosensitive resin composition was 70.7 mass% of propylene glycol monomethyl ether acetate in all the solvents, and propylene glycol monomethyl ether was 29.3 mass%. In addition, the ratio of binder resin (A2) and a polymeric compound (B) was 70/30 in conversion of solid content.

Example 7

[Preparation of photosensitive resin composition 7]

Colorant (E): C.I. Pigment Blue 15: 6 27 parts,

Colorant (E): C.I. 0.5 parts of Pigment Violet 23,

10 parts of an acrylic pigment dispersant,

8.3 parts of binder resin solution (A1) (solid content conversion), and

Propylene glycol monomethyl ether acetate 140 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

248 parts of binder resin solution (A1);

Polymerizable compound (B): dipentaerythritol hexaacrylate

35 parts of KAYARAD® DPHA (manufactured by Nihon Kayaku Co., Ltd.);

Polymerization initiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-

[Irgacure (R) OXE-01; BASF Japan Co., Ltd.] 5.8 parts;

Polymerization Initiator (C): 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

Lucirin® TPO; BASF Japan Co., Ltd.] 9.4 parts;

Polymerization initiator (C): Diethyl thioxanthone

4.7 parts [manufactured by KAYACURE® DETX-S Nihon Kayaku Co., Ltd.);

Solvent (D): 190 parts of propylene glycol monomethyl ethers

Solvent (D): 317 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Doore Dow Corning Co., Ltd.] 0.5 parts

Was mixed and the photosensitive resin composition 7 was obtained.

The solvent of the obtained photosensitive resin composition was 70.7 mass% of propylene glycol monomethyl ether acetate in all the solvents, and propylene glycol monomethyl ether was 29.3 mass%. In addition, the ratio of binder resin (A2) and a polymeric compound (B) was 70/30 in conversion of solid content.

Comparative Example 8

[Preparation of photosensitive resin composition 8]

Colorant (E): C.I. Pigment Green 36 55

Colorant (E): C.I. 24 pieces of Pigment Yellow 150,

10 parts of an acrylic pigment dispersant,

20 parts of binder resin solution (A3) (solid content conversion), and

Propylene glycol monomethyl ether acetate 260 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

46 parts of binder resin solution (A3) (solid content conversion);

Polymerizable compound (B): dipentaerythritol hexaacrylate

57 parts of KAYARAD® DPHA (manufactured by Nihon Kayaku Co., Ltd.);

Polymerization initiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-

[Irgacure (R) OXE-01; BASF Japan Co., Ltd.] 15 parts;

Polymerization Initiation Aids (C): 4,4'-Di (N, N-diethylamino) -benzophenone

[5 parts of EAB-F Hodogaya Kagaku Co., Ltd.];

Solvent (D): 500 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Toray Dow Corning Co., Ltd.] 0.5 parts;

Epoxy Resin: SUMI-EPOXY

6.1 parts of ESCN-195XL (manufactured by Sumitomo Chemical Co., Ltd.);

To obtain a photosensitive resin composition 8.

The solvent of the obtained photosensitive resin composition was 100 mass% of propylene glycol monomethyl ether acetate in all the solvents. In addition, the ratio of binder resin (A3) and a polymeric compound (B) was 46/57 in conversion of solid content.

Comparative Example 9

[Preparation of photosensitive resin composition 9]

Colorant (E): C.I. Pigment Blue 15: 6 27 parts,

Colorant (E): C.I. 0.5 parts of Pigment Violet 23,

10 parts of an acrylic pigment dispersant,

7.4 parts of binder resin solution (A1) (solid content conversion), and

Propylene glycol monomethyl ether acetate 140 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

274 parts of binder resin solution (A1);

Polymerizable compound (B): dipentaerythritol hexaacrylate

38 parts of KAYARAD (registered trademark) DPHA (manufactured by Nihon Kayaku Co., Ltd.);

Polymerization initiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-

[Irgacure (R) OXE-01; BASF Japan Co., Ltd.] 6.4 parts;

Polymerization initiator (C): Diethyl thioxanthone

2.6 parts of KAYACURE (registered trademark) DETX-S Nihon Kayaku Co., Ltd .;

Solvent (D): 489 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Doore Dow Corning Co., Ltd.] 0.5 parts

To obtain a photosensitive resin composition 9.

The solvent of the obtained photosensitive resin composition was 93.0 mass% of propylene glycol monomethyl ether acetate in the whole solvent, and was 7.0 mass% of propylene glycol monomethyl ether. In addition, the ratio of binder resin (A1) and a polymeric compound (B) was 70/30 in conversion of solid content.

Comparative Example 10

[Preparation of photosensitive resin composition 10]

Colorant (E): C.I. Pigment Blue 15: 6 27 parts,

Colorant (E): C.I. 0.5 parts of Pigment Violet 23,

10 parts of an acrylic pigment dispersant,

7.4 parts of binder resin solution (A4) (solid content conversion), and

Propylene glycol monomethyl ether acetate 140 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

197 parts of binder resin solution (A4);

Polymerizable compound (B): dipentaerythritol hexaacrylate

35 parts of KAYARAD® DPHA (manufactured by Nihon Kayaku Co., Ltd.);

Photoinitiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine

[Irgacure (R) OXE-01; BASF Japan Co., Ltd.] 5.8 parts;

Photoinitiator (C): bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Irgacure (R) 819; BASF Japan Co., Ltd.] 9.4 parts;

Polymerization initiator (C): Diethyl thioxanthone

4.7 parts [manufactured by KAYACURE® DETX-S Nihon Kayaku Co., Ltd.);

Solvent (F): 559 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Doore Dow Corning Co., Ltd.] 0.5 parts

To obtain a photosensitive resin composition 10.

The solvent of the obtained photosensitive resin composition was 100 mass% of propylene glycol monomethyl ether acetate in all the solvents. In addition, the ratio of binder resin (A1) and a polymeric compound (B) was 70/30 in conversion of solid content.

Comparative Example 11

[Preparation of Photosensitive Resin Composition 11]

Colorant (E): C.I. Pigment Blue 15: 6 27 parts,

Colorant (E): C.I. 0.5 parts of Pigment Violet 23,

10 parts of an acrylic pigment dispersant,

7.4 parts of binder resin solution (A5) (solid content conversion), and

Propylene glycol monomethyl ether acetate 140 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

171 parts of binder resin solution (A5);

Polymerizable compound (B): dipentaerythritol hexaacrylate

35 parts of KAYARAD® DPHA (manufactured by Nihon Kayaku Co., Ltd.);

Photoinitiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine

[Irgacure (R) OXE-01; BASF Japan Co., Ltd.] 5.8 parts;

Photoinitiator (C): bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

(Irgacure® 819; manufactured by BASF Japan) 9.4 parts;

Polymerization initiator (C): Diethyl thioxanthone

4.7 parts [manufactured by KAYACURE® DETX-S Nihon Kayaku Co., Ltd.);

Solvent (F): 584 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Doore Dow Corning Co., Ltd.] 0.5 parts

Was mixed and the photosensitive resin composition 11 was obtained.

The solvent of the obtained photosensitive resin composition was 100 mass% of propylene glycol monomethyl ether acetate in all the solvents. In addition, the ratio of binder resin (A1) and a polymeric compound (B) was 70/30 in conversion of solid content.

Comparative Example 12

[Preparation of Photosensitive Resin Composition 12]

Colorant (E): C.I. Pigment Blue 15:62 Part 27,

Colorant (E): C.I. 0.5 parts of Pigment Violet 23,

10 parts of an acrylic pigment dispersant,

8.3 parts of binder resin solution (A1) (solid content conversion), and

Propylene glycol monomethyl ether acetate 140 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

248 parts of binder resin solution (A1);

Polymerizable compound (B): dipentaerythritol hexaacrylate

35 parts of KAYARAD® DPHA (manufactured by Nihon Kayaku Co., Ltd.);

Polymerization Initiator (C): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine

[Irgacure (R) OXE-01; BASF Japan Co., Ltd.] 5.8 parts;

Polymerization initiator (C): bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Irgacure (R) 819; BASF Japan Co., Ltd.] 9.4 parts;

Polymerization initiator (C): Diethyl thioxanthone

4.7 parts [manufactured by KAYACURE® DETX-S Nihon Kayaku Co., Ltd.);

Solvent (D): 231 parts of propylene glycol monomethyl ether

Solvent (D): 275 parts of propylene glycol monomethyl ether acetate; And

Surfactant (F): polyether-modified silicone oil [doresilicon SH8400; Doore Dow Corning Co., Ltd.] 0.5 parts

Was mixed and the photosensitive resin composition 12 was obtained.

The solvent of the obtained photosensitive resin composition was 65.0 mass% of propylene glycol monomethyl ether acetate in all the solvents, and was 35.0 mass% of propylene glycol monomethyl ether. In addition, the ratio of binder resin (A1) and a polymeric compound (B) was 70/30 in conversion of solid content.

<Production of Patterned Coating Film>

The board | substrate was produced by bonding PET film (Lumira 75-T60 by Toray) on the square glass plate of one side 2 inches. The photosensitive resin composition obtained above was apply | coated to the PET film side of a board | substrate by the spin coat method, and it prebaked for 2 minutes at 80 degreeC on the hotplate. After cooling, the substrate coated with the curable composition was exposed to an exposure machine [TME-150RSK; Topcon Co., Ltd.] was irradiated to the whole surface of the board | substrate by the atmospheric amount and 150 mJ / cm <2> exposure amount (365 nm reference | standard). In addition, as a photomask, the thing in which the line-and-space pattern of 10-100 micrometers was formed was used. After light irradiation, the patterned coating film was obtained by immersing and developing with the aqueous developing solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide for 50 second at 23 degreeC, and wash | cleaning with pure water. The film thickness of the obtained patterned coating film was measured by a film thickness measuring apparatus [DEKTAK3; It was 2 micrometers when it measured using Nihon Shinku Co., Ltd. product.

<Evaluation of resolution>

The obtained patterned coating film was observed with the laser microscope (Axio Imager MAT Carl Zeiss company make), and the minimum dimension resolved was made into the resolution. The higher the resolution, the more usable for the production of high-definition color filters.

&Lt; Evaluation of development unevenness &

The obtained patterned coating film was observed with a laser microscope (manufactured by Axio Imager MAT Carl Zeiss Co., Ltd.), and evaluated that there was no water stain on the pattern as ○ (developing stains were not seen), and that water stain was found as × (developing stains). When development unevenness is seen, color unevenness arises when using for manufacture of a color filter.

<Evaluation of solvent resistance>

One milliliter of propylene glycol monomethyl ether acetate was added dropwise to the pattern formed on the substrate, and the mixture was kept at rest for 30 seconds and then rotated at a rotation speed of 1000 rpm for 10 seconds using a spin coater to remove the patterned propylene glycol monomethyl ether acetate .

The film thickness retention ratio was calculated from the film thickness values measured before and after the contact with propylene glycol monomethyl ether acetate according to the following formula. The higher the film thickness retention ratio is, the better the curability is, and when used in the production of a color filter, the color mixing can be prevented and the development unevenness is improved.

(Film thickness retention) (%) = (film thickness after contact) / (film thickness before contact)

<Production of Front Coating Film (Front Exposure Coating Film)>

The board | substrate was produced by bonding PET film (Lumira 75-T60 by Toray) on the square glass plate of one side 2 inches. The photosensitive resin composition obtained above was apply | coated to the PET film side of a board | substrate by the spin coat method, and it prebaked for 2 minutes at 80 degreeC on the hotplate. After cooling, the substrate coated with the curable composition was exposed to an exposure machine [TME-150RSK; Topcon Co., Ltd.] was irradiated to the whole surface of the board | substrate with the exposure amount (365 nm standard) of 150 mJ / cm <2> in air | atmosphere. In addition, the photomask was exposed to the whole surface, without using it. The film thickness of the obtained front coating film was measured by a film thickness measuring apparatus [DEKTAK3; It was 2 micrometers when it measured using Nihon Shinku Co., Ltd. product.

&Lt; Crosscut test >

About the obtained front coating film, the tape peeling test (crosscut test) based on JISK5600-5-6 was done, and the adhesiveness with PET film was evaluated. The results are shown in Table 1 and Table 2.

<Pencil hardness>

About the obtained front coating film, the measurement of the pencil hardness according to JIS-K 5400 was performed using the pencil scratch hardness tester (made by Yasuda Seiki Seisakusho). The load was 1,000 g.

&Lt; Evaluation of stickiness &

The photosensitive resin composition obtained above was apply | coated to the square PET film (Lumira 75-T60 by Toray, Ltd.) whose one side is 5 cm using the film applicator (AP75 made by Taiyuki Chemical Co., Ltd.), and on a hotplate, 80 Prebaked for 2 minutes at ° C. After cooling, the square PET film (Rohira 75-T60 manufactured by Toray) having 5 cm of uncoated one side was bonded to the surface to which the curable composition was applied, and then the square PET film having 5 cm of uncoated one side ( Toray Lumira 75-T60) was peeled off. The PET film to be coated has no stains, and the PET film to which it is not coated has no transfer. Adhesiveness). When adhesiveness is seen, color unevenness arises when using for manufacture of a color filter.

According to this invention, it becomes possible to provide the photosensitive resin composition which gives the pattern which has satisfactory hardness and adhesiveness.

By using the photosensitive resin composition of the present invention, it is possible to obtain a pattern with high resolution and improved unevenness in development. The pattern obtained by the present invention is useful as a display color filter for use in a liquid crystal display, an organic EL display, an electronic paper display, or the like.

Claims (11)

The photosensitive resin composition containing (A) binder resin, (B) polymeric compound, (C) polymerization initiator and starting adjuvant, and (D) solvent, The weight average molecular weight of (A) binder resin is 8,000 or more and 100,000 or less , (C) the polymerization initiator and the start aid contain at least an oxime compound, an acylphosphine oxide compound and a thioxanthone compound, and the solvent (D) has a solubility parameter of 8.0 to 9.1 (cal / cm 3) ^{1 /} Photosensitive resin which contains 70 mass% or more and 99 mass% or less of the ^2- phosphoric solvent, and contains 1 mass% or more and 30 mass% or less of the solvent with a solubility parameter of 9.2-11.0 (cal / cm <3>) ^1/2 . Composition. The photosensitive resin composition of Claim 1 whose solid acid value of (A) binder resin is 80 or more and 200 or less. The ratio of (A) binder resin and (B) polymeric compound is 50/50 or more of Claim 1 or 2, when it represents as (A) binder resin / (B) polymeric compound on a mass basis. Photosensitive resin composition which is / 20 or less. The photosensitive resin composition of any one of Claims 1-3 which further contains (E) coloring agent. The photosensitive resin composition of any one of Claims 1-4 which further contain (F) a leveling agent, and the quantity of a leveling agent is 0.001 mass% or more and 0.3 mass% or less. The patterned coating film formed of the photosensitive resin composition of any one of Claims 1-5. The process of apply | coating the photosensitive resin composition of any one of Claims 1-5 on a support body, removing a solvent, and forming a coating film, and
A method of producing a patterned coating film comprising the step of exposing the coating film after masking and removing an unexposed portion of the coating film with a developing solution. The process of apply | coating the photosensitive resin composition of any one of Claims 1-5 on a support body, removing a solvent, and forming a coating film, and
The manufacturing method of the patterned coating film which consists only of a process of exposing after exposing the said coating film and removing the unexposed part of the said coating film with a developing solution. The process of apply | coating the photosensitive resin composition of any one of Claims 1-5 on a support body, removing a solvent, and forming a coating film,
Exposing said coating film after masking and removing the unexposed part of said coating film with a developing solution, and
The manufacturing method of the patterned coating film containing the process of maintaining the coating film which removed the unexposed part with the developing solution at the temperature of 23 degreeC or more and 200 degrees C or less. The color filter containing the patterned coating film of Claim 6. The color filter containing the patterned coating film obtained by the manufacturing method in any one of Claims 7-9.