KR20070014998A - Photosensitive resin composition - Google Patents

Abstract

As a photosensitive resin composition containing binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), and a solvent (D), binder resin (A) consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride. A structural unit (A1) derived from at least one compound selected from the group, a structural unit (A2) derived from an unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group, and a structure Photosensitive which is a polymer (AA) containing the structural unit (A3) derived from the monomer copolymerizable with the unit (A1) and the structural unit (A2) (except the structural unit (A1) and the structural unit (A2)). Resin composition.

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition.

As the display device, a liquid crystal display, a plasma display, a paper-like display, a touch panel, and the like are known. Especially, the spacer is formed between the color filter which comprises a display apparatus, such as a liquid crystal display and a touch panel, and an array substrate, in order to maintain the space | interval of both board | substrates. Conventionally, spherical particles such as glass beads and plastic beads have been scattered and used as spacers.

However, when such spherical particles are used, the spherical particles are randomly scattered on the glass substrate, causing damage to a TFT element, an electrode, or the like, or when the spherical particles are present in the transmission pixel portion, the liquid crystal is scattered by incident light. The contrast of a display element may fall. Therefore, instead of using spherical particles, forming spacers with photosensitive resin has been proposed.

As a photosensitive resin used for spacer formation, although the composition for spacer formation containing the copolymer which consists of methacrylic acid, dicyclopentanyl methacrylate, and 2-hexahydrophthaloyloxyethyl methacrylate is known (Japanese Patent Laid-Open) Korean Patent Publication No. 10-319592, page 2, left column 2-page 2, left column 10), had a problem of poor solvent resistance.

MEANS TO SOLVE THE PROBLEM As a result of investigating the photosensitive resin composition with few problems as mentioned above, the photosensitive resin composition containing the binder resin which has a structural unit derived from the unsaturated compound which has an active methylene group and / or an active methine group is content. It was found that an excellent pattern could be formed.

The objective of this invention is providing the photosensitive resin composition which can form the pattern excellent in solvent resistance.

That is, this invention provides the following [1]-[5].

[One]. A photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the binder resin (A) is composed of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. Structural unit (A1) derived from at least 1 sort (s) of compound selected from (S), Structural unit (A2) derived from unsaturated compound which has at least 1 sort (s) of group selected from the group which consists of an active methylene group and an active methine group, and a structural unit Photosensitive resin which is a polymer (AA) containing (A1) and the structural unit (A3) derived from the monomer copolymerizable with a structural unit (A2), except a structural unit (A1) and a structural unit (A2). Composition.

[2]. The photosensitive resin composition as described in [1] whose unsaturated compound which has at least 1 sort (s) of group chosen from the group which consists of an active methylene group and an active methine group is a compound represented by Formula (I) or Formula (II).

[In formula (I) and formula (II), R <^1> represents a C1-C24 hydrocarbon group which may respectively contain a hydrogen atom or a hetero atom,

R <^2> represents a single bond or a C1-C20 bivalent hydrocarbon group,

R ³ represents a divalent group represented by any one of Formulas (1-1) to (1-3),

R ⁴ represents a group represented by any one of Formulas (1-4) to (1-7),

R ⁵ represents the same meaning as R ¹ ,

X represents a divalent group represented by any one of formulas (1-8) to (1-10).]

[3]. Structural unit derived from at least 1 sort (s) of compound chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride with respect to the total mole number of all the structural components which binder resin (A) comprises binder resin (A). 5 to 50 mol% of content of the structural unit (A2) derived from the unsaturated compound which has the content of (A1) is 5-40 mol%, the at least 1 group chosen from the group which consists of an active methylene group and an active methine group, and 10-90 mol% of content of the structural unit (A3) derived from the monomer copolymerizable with a structural unit (A1) and the structural unit (A2) (except structural unit (A1) and structural unit (A2)). The photosensitive resin composition as described in [1] or [2] which is a phosphorus copolymer (AA).

[4]. The pattern formed using the photosensitive resin composition in any one of [1]-[3].

[5]. The display apparatus containing the pattern of [4].

To practice the invention  Form for

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The photosensitive resin composition of this invention contains binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), and a solvent (D). The binder resin (A), the photopolymerizable compound (B) and the photopolymerization initiator (C) are usually dissolved or dispersed in the solvent (D).

The binder resin (A) used for the sensitive resin composition of this invention has alkali solubility, and is a structural unit (A1) derived from the at least 1 sort (s) of compound chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride. ), A structural unit (A2) derived from an unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group, and a compound and a structural unit (A2) for deriving the structural unit (A1) It is a polymer (AA) containing structural unit (A3) derived from the monomer copolymerizable with a compound (except structural unit (A1) and structural unit (A2).).

As at least 1 type of compound chosen from the group which consists of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride which guide | induce the said structural unit (A1), Specifically, unsaturated monocara, such as acrylic acid, methacrylic acid, a crotonic acid, etc. Acids;

Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

And anhydrides of the above unsaturated dicarboxylic acids;

Unsaturated mono [(meth) acryloyloxyalkyl of divalent or higher polyhydric carboxylic acid, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ] Esters;

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

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from copolymerization reactivity and solubility in aqueous alkali solution. These may be individual or may be used in combination of 2 or more type.

As an unsaturated compound which has at least 1 sort (s) of group chosen from the group which consists of an active methylene group and an active methine group which induce the said structural unit (A2), For example, the compound represented by Formula (I), Formula (II), etc. Can be mentioned.

In formula (I) and formula (II), R <^1> represents a C1-C24 hydrocarbon group which may respectively contain a hydrogen atom or a hetero atom independently.

R <^2> represents a single bond or a C1-C20 bivalent hydrocarbon group.

R ³ represents a divalent group represented by any one of Formulas (1-1) to (1-3).

R ⁴ represents a group represented by any one of Formulas (1-4) to (1-7).

R ⁵ has the same meaning as R ¹ .

X represents a divalent group represented by any one of formulas (1-8) to (1-10).]

R ¹ and R ⁵ are hydrogen atom, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, methoxy group, ethoxy group, propoxy group, hexoxy group, cyclohexoxy group, formula (1-11) It is preferable that it is group represented by-formula (1-13), and it is more preferable that it is a hydrogen atom and a methyl group.

R ² is preferably a single bond, a methylene group, an ethylene group, a propylene group, a butylene group, a propylene group, a hexylene group, a cyclohexylene group, an octylene group, a decylene group, a dodecylene group, and a single bond, a methylene group It is more preferable that it is an ethylene group.

As a compound represented by Formula (I), the following compounds etc. are mentioned specifically ,.

As a compound represented by Formula (II), the following compounds etc. are mentioned specifically ,.

Formulas (I-1) to (I-7), (I-16), (II-1), (II-2) and (II-5) each contain a structural unit derived from a methacryl group. However, the compound containing the structural unit derived from an acryl group can also be illustrated similarly.

Especially, as a compound which derives a structural unit (A2), 2- (methacryloyloxy) ethyl acetate acetate (compound represented by [formula (I-1)]) is preferable.

The at least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II) can be used independently, respectively, and can also mix and use in arbitrary ratios. When mixing, the mixing ratio is a molar ratio, and Formula (I): Formula (II) becomes like this. Preferably it is 5: 95-95: 5, More preferably, it is 10: 90-90: 10, More preferably, 20 : 80-80: 20.

Binder resin (A) contains the structural unit (A2) derived from the unsaturated compound which has at least 1 type of group chosen from the group which consists of an active methylene group and an active methine group, and obtains the coating film obtained from the photosensitive resin composition. The developability at the time of developing becomes favorable, and the solvent resistance of the pattern obtained by image development becomes favorable.

The monomer which guide | induces said structural unit (A3) is a monomer other than the monomer which guide | induces a structural unit (A1), and the monomer which guide | induces a structural unit (A2), and the monomer which guide | induces a structural unit (A3) is a structural unit It is a monomer which can superpose | polymerize with the monomer which derives (A1), and the monomer which derives a structural unit (A2). As a monomer which induces a structural unit (A3), specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (Meth) acrylic-acid alkylesters, such as (meth) acrylate;

Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6 ] decane-8-yl (meth) acrylate (in the art, dicyclopentanyl ( (Meth) acrylic acid cyclic alkyl esters such as meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, and isoboroyl (meth) acrylate;

(Meth) acrylic acid aryl esters, such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Acrylic acid aryl esters such as phenyl acrylate and benzyl 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;

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2 '-Hydroxyethyl) bicyclo [2.2.1] hepto-2-ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene , 5,6-dihydroxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5,6-di (hydroxymethyl) Bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-dimethoxybicyclo [2.2. 1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5- Hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2 .1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2 .2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene, 5 , 6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride), 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxy Cycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo [2.2 .1] bicyclo unsaturated compounds, such as hepto-2-ene and 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl- Dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate , 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hepto-2-ene and the like are reactive in copolymerization and solubility in aqueous alkali solution. Preferably used.

These may be individual or may be used in combination of 2 or more type.

The binder resin (A) used for this invention is a polymer (AA) containing a structural unit (A1), a structural unit (A2), and a structural unit (A3), and the ratio of the structural unit guide | induced from each is said air It is preferable to exist in the following ranges with a mole fraction with respect to the total mole number of the structural unit which comprises coalescence.

Structural units derived from (A1); 5-40 mol%

Structural units derived from (A2); 5-50 mol%

10 to 90 mol% of structural units derived from (A3)

Moreover, it is more preferable that the ratio of the said structural unit exists in the following ranges.

Structural units derived from (A1); 10 to 35 mol%

Structural units derived from (A2); 10 to 40 mol%

Structural units derived from (A3); 25 to 80 mol%

When the ratio of the structural unit is in the above range, the solvent resistance and developability tend to be further improved.

The binder resin (A) is described in, for example, the method described in "Experimental Method of Polymer Synthesis" (Otsu Takayuki Kogyo Co., Ltd., Chemical Copper, First Edition First Edition March 1, 1972) and the document. It can manufacture based on the cited document described.

Specifically, by placing a predetermined amount, a polymerization initiator and a solvent of each compound inducing each of the structural units (A1), (A2) and (A3) of the copolymer into the reaction vessel and replacing oxygen with nitrogen, the oxygen is absent. The polymer can be obtained by stirring, heating (for example, 50-140 degreeC), and heat-retaining (for example, 1 to 10 hours) under the following. Moreover, the obtained copolymer may use the solution after reaction as it is, or may use the concentrated or diluted solution, and what was taken out as solid (powder) by methods, such as reprecipitation, is melt | dissolved in a solvent, and is used again. You may also

The weight average molecular weight of polystyrene conversion of the said binder resin (A) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000. When the weight average molecular weight of a binder resin (A) exists in the said range, the applicability | paintability at the time of apply | coating the photosensitive resin composition containing this binder resin (A) tends to become favorable, and also the film | membrane decrease occurs at the time of image development. In addition, it is preferable because the missing property of the non-pixel portion tends to be good at the time of development.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (A) becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. When molecular weight distribution exists in the said range, since it exists in the tendency which is excellent in developability, it is preferable.

Content of binder resin (A) used for the photosensitive resin composition of this invention is mass fraction with respect to solid content in the photosensitive resin composition, Preferably it is 5-90 mass%, More preferably, it is 10-70 mass%. When content of binder resin (A) exists in the said range, solubility to a developing solution is enough, the development residue does not generate | occur | produce well on the board | substrate of a non-pixel part, and the film | membrane reduction of the pixel part of an exposure part occurs well at the time of image development. It is not preferable because the missing property of the non-pixel portion tends to be good. Here, solid content of the photosensitive resin composition means the thing except the component which shows a liquid at normal temperature among the solvent component in the photosensitive resin composition and the additive which can be added arbitrarily.

Moreover, as long as it is a range which does not impair the effect of this invention, you may use together the acrylic binder resin normally used in this field.

As a photopolymerizable compound (B) used for this invention, a monofunctional monomer, a bifunctional monomer, and a trifunctional or more than trifunctional polyfunctional monomer are mentioned.

As a specific example of a monofunctional monomer, nonylphenyl carbitol acrylate, 2-hydroxy-3- phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrroli Money, etc.

As a specific example of a bifunctional monomer, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol Bis (acryloyloxyethyl) ether of A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

As a specific example of a trifunctional or more than trifunctional monomer, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate And reactants of dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride, reactants of dipentaerythritol penta (meth) acrylate and acid anhydride, and the like. In these, a bifunctional monomer or a trifunctional or more than trifunctional monomer is used preferably. These photopolymerizable compounds (B) may be individual or may be used together 2 or more types.

Content of a photopolymerizable compound (B) is mass fraction with respect to the total amount of binder resin (A) and a photopolymerizable compound (B), Preferably it is 1-70 mass%, More preferably, it is 5-60 mass%. When content of a photopolymerizable compound (B) exists in the said range, since the intensity | strength, smoothness, and reliability of a pixel part tend to become favorable, it is preferable.

Examples of the photopolymerization initiator (C) used in the present invention include acetophenone series, biimidazole series, oxime series, triazine series, acylphosphine oxide series and organic boron salt initiators. Since the photosensitive resin composition obtained by using a photoinitiator adjuvant (C-1) together by these photoinitiators (C-1) becomes more sensitive, productivity of a pattern will be formed when using a photoinitiator adjuvant (C-1) together and forming a pattern. It is preferable because this is improved.

As said acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2 -Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 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-morpholinophenyl) -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-dimethyl Vagin) -2-dimethylamino-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-morpholi Nophenyl) -butanone, 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-methoxy Benzyl) -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-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2 -Bro -4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane And oligomers of -1-ones.

As said biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3, for example). -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, 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, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.). .), An imidazole compound in which the phenyl group in the 4,4'5,5'-position is substituted with a carboalkoxy group (see, for example, JP-A-7-10913, etc.); , Preferably 2,2'-bis (2-chloro Rophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole Can be mentioned.

As said oxime compound, O-ethoxycarbonyl- (alpha)-oxyimino-1- phenyl propane- 1-one, the compound represented by Formula (P3), the compound represented by Formula (P4), etc. are mentioned, for example. Can be.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl), for example. -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 acylphosphine oxide type initiator, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned, for example.

As said organic boron salt initiator, For example, tetramethylammonium n-butyl triphenyl borate, tetraethylammonium isobutyl triphenyl borate, tetra n-butylammonium n-butyl tri (4-tert- butylphenyl) borate, Tetra n-butylammonium n-butyl trinaphthyl borate, tetra n-butyl ammonium methyl tri (4-methylnaphthyl) borate, triphenylsulfonium n-butyl triphenyl borate, triphenyloxosulfonium n-butyl triphenyl Borate, triphenyl oxonium n-butyl triphenyl borate, N-methylpyridium n-butyl triphenyl borate, tetraphenyl phosphonium n-butyl triphenyl borate, diphenyl iodonium n-butyl triphenyl borate, etc. are mentioned. have.

Moreover, the photoinitiator etc. which are normally used in this field can be used together, and as said photoinitiator, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. have.

More specifically, the following compounds are mentioned, These may be individual, respectively and may be used in combination of 2 or more type.

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, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-, for example 4-propoxy city oxanthone 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. Can be mentioned.

In addition, photopolymerization initiators such as 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds can also be used. .

Moreover, the photoinitiator described in Unexamined-Japanese-Patent No. 2002-544205 can also be used as a photoinitiator which has group which can cause chain transfer.

As a photoinitiator which has the group which can cause the said chain transfer, the photoinitiator etc. represented by Formula (P5)-(P10) are mentioned, for example.

The photoinitiator which has the group which can cause the said chain transfer can be used also as a structural component (A3) of the said copolymer. And the obtained copolymer can be used as binder resin used for the photosensitive resin composition of this invention, and can also be used together with binder resin (A).

It is preferable to use photopolymerization start adjuvant (C-1) in combination for a photoinitiator (C). As a photoinitiator, it is preferable that an amine compound and the following carboxylic acid compound are preferable, and an aromatic amine compound is more preferable.

Specific examples of the photopolymerization start adjuvant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate isoamyl and 4-dimethyl Aminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, etc. Aromatic amine compound is mentioned.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid and chlorophenylthio. And aromatic heteroacetic acids such as acetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

Content of a photoinitiator (C) is mass fraction with respect to the total amount of binder resin (A) and a photopolymerizable compound (B), Preferably it is 0.1-40 mass%, More preferably, it is 1-30 mass%.

In addition, content of a photoinitiator adjuvant (C-1) is a mass fraction with respect to the total amount of binder resin (A) and a photopolymerizable compound (B), Preferably it is 0.01-50 mass%, More preferably, it is 0.1- 40 mass%.

When the total amount of photoinitiator (C) is in the said range, since the photosensitive resin composition becomes high sensitivity, the intensity | strength of the pixel part formed using the said photosensitive resin composition and the smoothness in the surface of the said pixel tend to become favorable. desirable. In addition to the above, when the amount of the photopolymerization initiation assistant (C-1) is in the above range, the sensitivity of the obtained photosensitive resin composition is further increased, and the productivity of the patterned substrate formed using the photosensitive resin composition tends to be improved. desirable.

As the solvent (D) used in the present invention, various organic solvents used in the field of the photosensitive resin composition can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether and diethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate;

Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether;

Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate and dipropylene glycol monopropyl ether acetate;

Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

 Of the solvents described above, in view of coatability and dryness, preferably an organic solvent having a boiling point of 100 to 200 is used in the solvent, and more preferably alkylene glycol alkyl ether acetates, ketones and ethyl 3-ethoxypropionate. And esters such as methyl 3-methoxypropionate are used, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate ethyl, and 3-methoxypropionate methyl Used.

These solvents (D) may be individual and may be used in mixture of 2 or more types.

Content of the solvent (D) in the photosensitive resin composition of this invention is a mass fraction with respect to the photosensitive resin composition, Preferably it is 60-90 mass%, More preferably, it is 70-85 mass%. When content of the solvent (D) exists in the said range, applicability | paintability is favorable when apply | coated with the coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater (it may also be called a die coater and a curtain flow coater), and inkjet. It is preferable because it tends to be lost.

In the photosensitive resin composition of this invention, additives, such as a filler, another high molecular compound, a pigment dispersing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, a chain transfer agent, an acid generator, and a base generator, can also be used together as needed. have.

A filler may be added for adjustment or coloring of coating film strength, and glass, silica, alumina, a pigment, etc. are specifically mentioned as said filler.

Another polymeric compound may be added for adjustment of coating film strength. Specific examples of other high molecular compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkylacrylates, polyesters, polyurethanes, and the like. Is illustrated.

As the pigment dispersant, commercially available surfactants can be used, and for example, surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric and the like can be cited. You may use in combination of 2 or more type. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, In addition to polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoe Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), Mega Park (Dainippon Ink Chemical Co., Ltd.) Co., Ltd.), Floride (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Saffron (above, Asahi Glass Co., Ltd.), Solpas (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co. ) And PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.).

An adhesion promoter may be added in order to improve adhesiveness with a board | substrate or a base material, As a said adhesion promoter, specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane , 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. are mentioned.

Antioxidant may be added in order to prevent deterioration by oxidation of a coating film, and as said antioxidant, 2,2'- thiobis (4-methyl-6-tert- butylphenol), 2, 6-di-tert-butyl-4-methylphenol etc. are mentioned.

A ultraviolet absorber may be added in order to prevent deterioration by the ultraviolet-ray of a coating film, and specifically, as said ultraviolet absorber, 2- (3-tert- butyl- 2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole And alkoxy benzophenones.

A chain transfer agent may be added for molecular weight control in a curing reaction, and dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, etc. are mentioned as said chain transfer agent.

The acid generator may be added as a curing reaction catalyst, and as the acid generator, an aryldiazonium salt, a diaryl iodonium salt, a triarylsulfonium salt, a triarylsulfonium salt, a pyridinium salt, a quinolinium salt, and an isoqui Nolinium salts, sulfonic acid esters, iron arene complexes and the like.

A base generator may be added as a curing reaction catalyst, and as the base generator, 1-methyl-1- (4-biphenylyl) ethylcarbamate and 1,1-dimethyl-2-cyanoethylcarba Carbamate derivatives such as mate, urea derivatives such as urea and N, N-dimethyl-N'-methyl urea, dihydropyridine derivatives such as 1,4-dihydronicotinamide, quaternary ammonium salts of organic silane and organic borane And compounds such as benzoylcyclohexylcarbamate and triphenylmethanol described in JP-A 4-162040, such as dicyandiamide, compounds described in JP-A 5-158242, and the like. have.

The photosensitive resin composition can be apply | coated on a base material as follows, for example, can photocure and develop, and can form a pattern. First, the composition is applied onto a substrate (usually glass) or a layer composed of solids of the photosensitive resin composition formed first to obtain a photosensitive resin composition layer, and prebaking the photosensitive resin composition layer to remove volatile components such as solvents. To get a smooth coating. The thickness of the coating film at this time is about 1-6 micrometers. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated to the whole exposure part uniformly, and a mask and a board | substrate may be correctly aligned. In addition, the target pattern shape can be obtained by making the coating film after an exposure process contact with aqueous alkali solution, melt | dissolving, and developing. The developing method may be any of a liquid stacking method, a dipping method, a spray method, and the like. In addition, you may incline a board | substrate at arbitrary angles at the time of image development.

The developing solution used for image development after patterning exposure is the aqueous solution containing an alkaline compound and surfactant normally.

The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

Moreover, as an example of an organic alkaline compound, tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds may be individual, respectively, and may be used in combination of 2 or more type. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be any of nonionic surfactants, anionic surfactants or cationic surfactants.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, and sorbitan fatty acid esters. , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and sodium dodecylbenzenesulfonate And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethyl ammonium chloride, or quaternary ammonium salts.

These surfactant may be used independently, respectively and may be used in combination of 2 or more type.

The concentration of the surfactant in the alkaline developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.

After image development, water washing is performed and 10-60 minutes post-baking can also be performed in the temperature range of 150-230 degreeC further as needed.

Using the photosensitive resin composition of this invention, a pattern can be formed on a board | substrate or a color filter substrate through each above process. This pattern is useful as a photo spacer used for a liquid crystal display device. In addition, when the photomask for hole formation is used at the time of patterning exposure with respect to a dry coating film, a hole can be formed and it is useful as an interlayer insulation film. Furthermore, at the time of exposure to a dry coating film, a transparent film can be formed only by whole surface exposure, heat hardening, or heat hardening, without using a photo mask, and this transparent film is useful as an overcoat.

By forming the pattern obtained in this way in display apparatuses, such as a liquid crystal display device, the display apparatus of the outstanding quality can be manufactured with high yield.

The photosensitive resin composition of this invention can form patterns and coating films, such as a spacer excellent in solvent resistance, and can resolve to a fine pattern.

The photosensitive resin composition of this invention can be used suitably mainly as a pattern formation material.

Example

Hereinafter, although this invention is demonstrated in detail based on an Example, it cannot be overemphasized that this invention is not limited by these Examples. In Examples,% and part which show content-usage-amount are a mass reference | standard unless there is particular notice.

Synthesis Example 1

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.03 L / min to make a nitrogen atmosphere, and 34.92 parts by mass of propylene glycol monomethyl ether acetate was added thereto and heated to 90 ° C while stirring. Next, 6.89 parts by mass of methacrylic acid, 34.28 parts by mass of 2- (methacryloyloxy) ethylacetate and 28.68 parts by mass of N-cyclohexylmaleimide, the polymerization initiator 2,2'-azobis (isobutyronitrile) 3.28 parts by mass was dissolved in 69.84 parts by mass of propylene glycol monomethyl ether acetate to prepare a solution, and the solution was added dropwise into a flask kept at 90 ° C. over 1 hour from a dropping funnel. After dripping of this solution was complete | finished, it hold | maintained at 90 degreeC for 4 hours, and cooled to room temperature after that, and obtained the solution of copolymer (resin Aa). The weight average molecular weight (Mw) of obtained resin Aa was 14,300, and the dispersion degree was 2.45.

Synthesis Example 2

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.03 L / min to form a nitrogen atmosphere, and 33.06 parts by mass of propylene glycol monomethyl ether acetate was added and heated to 90 ° C while stirring. Next, 10.33 parts by mass of methacrylic acid, 34.28 parts by mass of 2- (methacryloyloxy) ethylacetate and 21.51 parts by mass of N-cyclohexyl maleimide, the polymerization initiator 2,2'-azobis (isobutyronitrile) 3.28 parts by mass was dissolved in 66.11 parts by mass of propylene glycol monomethyl ether acetate to prepare a solution, and the dissolved solution was added dropwise into a flask kept at 90 ° C. over 1 hour from a dropping funnel. After dripping of this solution was complete | finished, it hold | maintained at 90 degreeC for 4 hours, and cooled to room temperature after that, and obtained the solution of a copolymer (resin Ab). The weight average molecular weight of obtained resin Ab was 11,900, and dispersion degree was 2.37.

Synthesis Example 3

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.03 L / min to make a nitrogen atmosphere, and 63.31 parts by mass of propylene glycol monomethyl ether acetate was added thereto and heated to 90 ° C while stirring. Next, 20.66 parts by mass of methacrylic acid, 34.28 parts by mass of 2- (methacryloyloxy) ethylacetate and 71.69 parts by mass of N-cyclohexylmaleimide, the polymerization initiator 2,2'-azobis (isobutyronitrile) 6.57 parts by mass was dissolved in 171.85 parts by mass of propylene glycol monomethyl ether acetate to prepare a solution, and the solution was added dropwise into a flask kept at 90 ° C. over 1 hour from a dropping funnel. After dripping of this solution was complete | finished, it hold | maintained at 90 degreeC for 4 hours, and cooled to room temperature after that, and obtained the solution of a copolymer (resin Ac). The weight average molecular weight of obtained resin Ac was 13,900, and the dispersion degree was 2.67.

Synthesis Example 4

Resin Ad was obtained by operation similar to the synthesis example 1 of Unexamined-Japanese-Patent No. 11-133600. Specifically, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol dimethyl ether were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 30 parts by weight of styrene, 20 parts by weight of methacrylic acid, and 50 parts by weight of glycidyl methacrylate were substituted for nitrogen, and stirring was started slowly. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a resin Ad. The weight average molecular weight of obtained resin Ad was 20,000, and dispersion degree was 2.85.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the said binder polymer, it carried out on condition of the following using GPC method.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0ml / min

Detectors; RI

The ratio of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into dispersion degree (Mw / Mn).

Example 1

40 parts of dipentaerythritol hexaacrylate and 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1- to a resin solution portion (60 parts in terms of solid content) containing the resin Aa obtained in Synthesis Example 1 7 parts of ON, 157 parts of propylene glycol monomethyl ether acetate, and 18 parts of 3-ethoxyethyl propionate were mixed to obtain a photosensitive resin composition (1).

Photosensitive Resin Composition 1 Photosensitive Resin Composition 2 Photosensitive Resin Composition 3 Photosensitive Resin Composition 4 Photosensitive Resin Composition 5 Binder Resin (A) Resin Aa (solid content only) 60 50 60 Resin Ab (solid content only) 30 Resin Ac (Solid Part Only) 30 Resin Ad (solid content only) 60 Photopolymerizable Compound (B) Dipentaerythritol hexaacrylate Nippon Gunpowder Co., Ltd. KAYARAD DPHA 40 50 40 40 40 Photopolymerization Initiator (C) 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (Irgacure-907 by CIBA SPECIALTY CHEMICALS) 7 7 7 7 Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by CIBA SPECIALTY CHEMICALS) 7 Solvent (D) Propylene Glycol Monomethyl Ether Acetate 157 157 157 157 3-ethoxyethylpropionate 18 18 18 18 Diethylene glycol dimethyl ether 197

A 2 inch square glass substrate (# 1737; manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the photosensitive resin composition (1) is exposed by the exposure amount (365 nm) of 100 mJ / cm <2>, spin-coated so that the film thickness after image development, water washing, and postbaking may be set to 3.0 micrometers, and then in a clean oven And prebaked at 100 ° C for 3 minutes. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass photomask was 50 μm, and the exposure amount was 100 mJ / cm 2 under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). The light was irradiated at (365 nm standard).

In addition, as a photo mask, the photo mask in which the following patterns were formed on the same plane was used.

ㆍ one side has a square light-transmitting part (pattern) of 20 micrometers, and the space | interval of the said square is 100 micrometers

After light irradiation, the said coating film was immersed in 23 degreeC for 80 second in aqueous developing solution containing 0.12 mass% of nonionic surfactant and 0.05 mass% of potassium hydroxide, and it post-baked for 20 minutes in 220 degreeC in oven after washing with water. Was performed. After cooling, the film thickness was measured.

About the photosensitive resin composition (1), storage stability was evaluated and the result was shown in Table 2. In addition, using the photosensitive resin composition (1), except having not used a photo mask, it carried out similarly to the above, and produced the cured film and evaluated the following items.

Transparency (permeability (%)); Except not using a photo mask in an exposure process, the same operation as the above is performed, and the film thickness of the cured film produced so that it may become 2.9-3.1 micrometers in thickness is measured by a film thickness measuring apparatus (DEKTAK3; Nihon Vacuum Technology Co., Ltd.) Production).

Subsequently, the obtained cured film was measured using the microscopic spectrophotometer (OSP-SP200; Olympus Co., Ltd.), and the transmittance | permeability (%) in 400 nm is converted into the transmittance | permeability when it is set as film thickness 3.0 micrometers. It is described in Table 2.

Surface smoothness, line width, tapered shape (cross section); About the obtained cured film, it observed and measured using the scanning electron microscope (S-4000; the Hitachi Corporation make).

About the pattern resolution, it evaluated as what was resolved (circle) and the thing which was not resolved by x in the 20 micrometers pattern on a photomask.

Solvent resistance; In the exposure process, the same operation was carried out except that no photo mask was used, a coating film was produced, and the film thickness and transmittance were measured. The produced coating film was immersed in 30 degreeC N-methylpyrrolidone for 30 minutes, the film thickness and transmittance | permeability after immersion were measured, and those changes were calculated | required according to following Formula.

Film thickness retention rate (%); (Film thickness after immersion (μm) / film thickness before immersion (μm)) × 100

Permeability retention rate (%): (transmittance rate (%) after immersion / transmittance rate (%) before immersion) × 100

When the film thickness retention rate and the transmittance retention rate are 102% or less, respectively, the film thickness retention ratio is ×. It is shown in Table 2.

Adhesion; On the coating film after immersion in the solvent resistance test, 100 squares whose side was 1 mm were produced using the commercially available cutter knife. Peeling test was done using the commercially available cellophane tape. [(Number of squares left on the substrate without peeling) / 100] is shown in Table 2. The larger the value, the better the adhesion and the better.

Heat resistance; In the exposure process, the same operation was performed except not using a photo mask, and the coating film was produced. The produced coating film was left to stand in a 240 degreeC clean oven for 1 hour, the film thickness and transmittance | permeability (measurement wavelength; 400 nm) before and behind heating were measured, and those changes were calculated | required according to following Formula.

Film thickness retention rate (%); (Film thickness after heating (μm) / film thickness before heating (μm)) × 100

Transmittance retention (%); (Transmittance (%) after heating / transmittance (%) before heating) × 100

Adhesion; On the coating film after the heating in the heat resistance test, 100 squares whose side was 1 mm were produced using the commercially available cutter knife. Peeling test was done using the commercially available cellophane tape. [(Number of squares left on the substrate without peeling) / 100] is shown in Table 2. The larger the value, the better the adhesion and the better.

Example 2

The photosensitive resin composition (2) was obtained like the photosensitive resin composition (1) so that it might become the composition shown in Table 1, and it evaluated. The results are shown in Table 2.

Example 3

In the same manner as in Example 1, the photosensitive resin composition (3) was obtained so as to have the composition shown in Table 1, and it was evaluated. The results are shown in Table 2.

Example 4

In the same manner as in Example 1, the photosensitive resin composition (4) was obtained so as to have the composition shown in Table 1, and it was evaluated. The results are shown in Table 2.

Comparative Example 1

In the same manner as in Example 1, the photosensitive resin composition (5) was obtained so as to have the composition shown in Table 1, and it was evaluated. The results are shown in Table 2.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Photosensitive resin composition One 2 3 4 5 Surface smoothness ○ ○ ○ ○ ○ Transparency Transmittance (%) 96.2 96.2 97.5 96.2 95.8 pattern Line width (㎛) 22.6 27.0 20.1 20.2 21.3 Resolution ○ ○ ○ ○ ○ Tapered shape Forward taper Forward taper Forward taper Forward taper Forward taper Solvent resistance Permeability retention rate (%) 100 100 100 100 100 Film thickness retention rate (%) 101 101 101 101 105 Adhesion 100/100 100/100 100/100 100/100 100/100 Heat resistance Permeability retention rate (%) 95 93 96 97 93 Film thickness retention rate (%) 93 94 96 93 94 Adhesion 100/100 100/100 100/100 100/100 100/100

When the photosensitive resin composition of this invention containing a binder resin (A) is used from the result of Examples 1-4 shown in Table 2, it turns out that the pattern and coating film which are excellent in solvent resistance, a pattern shape, surface smoothness, and heat resistance are obtained. have. On the other hand, in the photosensitive resin composition containing the binder resin which does not correspond to the binder resin (A) contained in the photosensitive resin composition of this invention of the comparative example 1, only the pattern and the coating film which are inferior to solvent resistance were obtained.

By using the photosensitive resin composition of this invention, it is possible to form the pattern and coating film which are excellent in pattern shape, surface smoothness, heat resistance, and solvent resistance, and the film thickness of an overcoat, a photo spacer, an insulating film, the liquid crystal aligning control process, and a coloring pattern It can be used suitably for formation of the transparent film used for a display apparatus, such as a coating layer for joining together.

Claims (5)

A photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), wherein the binder resin (A) is composed of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. Structural unit (A1) derived from at least 1 sort (s) of compound selected from (S), Structural unit (A2) derived from unsaturated compound which has at least 1 sort (s) of group selected from the group which consists of an active methylene group and an active methine group, and a structural unit Photosensitive resin which is a polymer (AA) containing (A1) and the structural unit (A3) derived from the monomer copolymerizable with a structural unit (A2), except a structural unit (A1) and a structural unit (A2). Composition. The method of claim 1, The photosensitive resin composition whose unsaturated compound which has at least 1 sort (s) of group chosen from the group which consists of an active methylene group and an active methine group is a compound represented by Formula (I) or Formula (II).

[In formula (I) and formula (II), R <^1> represents a C1-C24 hydrocarbon group which may respectively contain a hydrogen atom or a hetero atom, R <^2> represents a single bond or a C1-C20 bivalent hydrocarbon group, R ³ represents a divalent group represented by any one of Formulas (1-1) to (1-3),

R ⁴ represents a group represented by any one of Formulas (1-4) to (1-7),

R ⁵ represents the same meaning as R ¹ , X represents a divalent group represented by any one of formulas (1-8) to (1-10).]

The method according to claim 1 or 2, Structural unit derived from at least 1 sort (s) of compound chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride with respect to the total mole number of all the structural components which binder resin (A) comprises binder resin (A). 5 to 50 mol% of content of the structural unit (A2) derived from the unsaturated compound which has the content of (A1) is 5-40 mol%, the at least 1 group chosen from the group which consists of an active methylene group and an active methine group, and 10-90 mol% of content of the structural unit (A3) derived from the monomer copolymerizable with a structural unit (A1) and the structural unit (A2) (except structural unit (A1) and structural unit (A2)). Phosphorus copolymer (AA) Phosphorus photosensitive resin composition. The pattern formed using the photosensitive resin composition of any one of Claims 1-3. A display device comprising the pattern of claim 4.