WO2012086610A1

WO2012086610A1 - Photosensitive resin composition, partition wall, color filter, and organic el element

Info

Publication number: WO2012086610A1
Application number: PCT/JP2011/079420
Authority: WO
Inventors: 高橋　秀幸; 健二石関; 川島　正行; 正樹小尾
Original assignee: 旭硝子株式会社
Priority date: 2010-12-20
Filing date: 2011-12-19
Publication date: 2012-06-28
Also published as: KR20140001915A; CN103261968A; JPWO2012086610A1; KR101817378B1; TW201232178A; JP5880445B2

Abstract

Provided is a photosensitive resin composition for forming a partition wall by a photolithography method, which is capable of forming a pattern with high resolution by improving adhesion of the pattern during the development. Also provided are: a partition wall which is formed as a pattern with high resolution; a color filter with high resolution, which uses the partition wall; and an organic EL element which uses the partition wall. Specifically provided are: a photosensitive resin composition for forming a partition wall by a photolithography method, said partition wall being arranged on a substrate so as to define a plurality of sections for the formation of pixels, which contains (A) a binder resin, (B) a photoactive agent, (C) fine particles that have a zeta potential of from -100 mV to -5 mV in a dispersion liquid as determined by an electrophoretic light scattering method, and (D) an organic solvent; a partition wall which is formed using this composition; a color filter which comprises the partition wall; and an organic EL element which comprises the partition wall.

Description

Photosensitive resin composition, partition, color filter, and organic EL device

The present invention relates to a photosensitive resin composition for forming partition walls by a photolithography method, partition walls formed using the same, a color filter having the partition walls, and an organic EL element.

In recent years, partition walls between pixels of a color filter, partition walls between pixels of an organic EL (Electro-Luminescence) element, partition walls between elements of an organic EL illumination, partition walls that partition each TFT of an organic TFT (Thin Film Transistor) array, As a material for forming a permanent film such as a partition wall of an ITO electrode of a liquid crystal display element and a partition wall of a circuit wiring board, a photosensitive resin composition has attracted attention.

When forming the partition of an optical element using such a photosensitive resin composition, the partition is patterned by a photolithography method on a transparent substrate such as glass. Then, an optical element is manufactured by forming a pixel in an opening between partition walls formed on the substrate. In the present specification, the “pattern” represents a shape of the partition as viewed from above the substrate.

In the photosensitive resin composition for forming a partition wall used in the production of the optical element, in order to obtain a pattern realizing high resolution, good photosensitivity and developability are required, and the production process, specifically In the manufacturing process performed in the order of coating, pre-baking, exposure, development, and post-baking, pattern adhesion during development and pattern dimension stability during post-baking are important points, and in recent years, attention has been focused on them. R & D is underway.

For example, in Patent Document 1, a resin composition in which a filler and a dispersant are blended together with a binder resin is proposed in order to prevent the shape of the partition wall from being deformed by thermal sag during post-baking. Patent Document 2 discloses a photosensitive resin composition that has excellent pattern dimensional stability, good development margin and good adhesion to partition walls, and maintains surface smoothness after post-baking among black matrixes. As a product, there has been proposed a photosensitive resin composition for a black resist containing a photocurable resin and a light-shielding pigment, and further containing granular silica having a specific particle diameter in a specific ratio with respect to the light-shielding pigment. However, in these examples, it is not always possible to obtain a pattern having a sufficiently high resolution.

Further, for the purpose different from the above, a filler other than the color pigment is also blended in the photosensitive resin composition for forming a partition wall. For example, Patent Document 3 describes a technique of a photosensitive resin composition containing an ink repellent agent for forming a partition, which is used when an optical element is manufactured by forming pixels by an inkjet method. However, here, by using a photosensitive resin composition for forming a partition wall in which fine particles having a specific particle diameter are blended, ink mixing can be prevented by forming fine holes in the partition wall and absorbing the ink solvent. .

Further, in Patent Document 4, fine particles, particularly negatively charged, are added to a photosensitive resin composition for forming partition walls in which a black pigment and a polymer dispersant having a basic functional group for dispersing the black pigment are blended. It is described that by adding fine particles, partition walls having sufficient liquid repellency can be obtained and ink color mixing can be prevented.
However, in the photosensitive resin composition for forming partition walls described in Patent Document 3 and Patent Document 4, although the ink repellency is improved by blending fine particles, a pattern with particularly high resolution can be obtained. I don't mean.

JP 2006-284673 A JP 2008-304583 A JP 2006-163233 A International Publication No. 2008/13312

The present invention has been made from the above viewpoint, and in a photosensitive resin composition for forming a partition wall by a photolithography method, a high-resolution pattern can be formed by improving the development adhesion of the partition wall. An object of the present invention is to provide a photosensitive resin composition. It is another object of the present invention to provide a partition wall formed as a high resolution pattern, a high resolution color filter using the partition wall, and an organic EL element.

The present invention provides a photosensitive resin composition, partition walls, a color filter, and an organic EL device having the following configurations [1] to [12].
[1] A photosensitive resin composition for forming a partition disposed in a form of partitioning a plurality of pixels on a substrate by a photolithography method, which includes a binder resin (A) and a photoactivator (B) A fine particle (C) in a dispersion using an organic solvent as a dispersion medium, and the zeta potential of the fine particle (C) in the dispersion measured by electrophoretic light scattering is −100 to −5 mV. A photosensitive resin composition comprising fine particles (C) and an organic solvent (D) at least part of which is an organic solvent of the dispersion.
[2] The photosensitive resin composition according to [1], wherein the fine particles (C) have an average particle size of 5 to 100 nm.
[3] The dispersion medium in the dispersion liquid of the fine particles (C) is an organic solvent having an SP value of 9 to 20 (cal / cm ³ ) ^1/2 having at least one hydroxyl group, [1] or [2] The photosensitive resin composition as described in 2.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the fine particles (C) are silica fine particles.
[5] The photosensitive resin composition according to [4], wherein the silica fine particles are colloidal silica.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the content of the fine particles (C) is 3 to 35% by mass with respect to the total solid content of the composition.
[7] The photosensitive resin composition according to any one of [1] to [6], further comprising a colorant (E).
[8] The photosensitive property according to [7], wherein the colorant (E) is at least one selected from the group consisting of carbon black, titanium black, a black metal oxide pigment, a silver tin alloy, and an organic pigment. Resin composition.
[9] The photosensitive resin composition according to any one of [1] to [8], wherein the partition wall formation surface of the substrate has surface characteristics having good affinity with an alkali developer used in the photolithography method.

[10] A partition formed in the form of dividing the substrate into a plurality of sections for pixel formation, and using the photosensitive resin composition according to any one of [1] to [9] by a photolithography method A partition characterized by being formed.
[11] A color filter having a plurality of pixels on a substrate and a partition located between adjacent pixels, wherein the partition is the partition according to [10].
[12] An organic EL element having a plurality of pixels and a partition located between adjacent pixels on the substrate, wherein the partition is the partition described in [10].

According to the present invention, there is provided a photosensitive resin composition capable of forming a high-resolution pattern by improving the development adhesion of the partition in the photosensitive resin composition for forming the partition by a photolithography method. it can. Moreover, the partition formed as a pattern with high resolution using this photosensitive resin composition, the high-resolution color filter using this, and an organic EL element can be provided.

It is a figure which shows typically the process of forming a partition using the photosensitive resin composition of this invention. It is a figure which shows the measurement position of the ink layer thickness for evaluating the ink layer uniformity at the time of forming a pixel using the partition for inkjets by the photosensitive resin composition of this invention.

Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments.
In the present specification, unless otherwise specified,% represents mass%. The (meth) acryloyl group is used as a general term meaning both an acryloyl group and a methacryloyl group.
Moreover, the composition after the organic solvent (D) is removed from the photosensitive resin composition (composition containing the organic solvent (D)) is referred to as a photosensitive composition. When the photosensitive resin composition contains a low-boiling component similar to the organic solvent (D), the photosensitive composition is a composition from which the low-boiling component has also been removed. This photosensitive composition also corresponds to the solid content of the photosensitive resin composition.
Furthermore, the film | membrane (film | membrane of the composition containing the organic solvent (D)) of the photosensitive resin composition obtained by apply | coating the photosensitive resin composition to the surface of a base material etc. is called a wet film | membrane. Moreover, the film | membrane of the photosensitive composition obtained by removing volatile components, such as an organic solvent (D), from a wet film | membrane is also called a photosensitive film | membrane.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention is a photosensitive resin composition for forming, by a photolithographic method, a partition disposed on a substrate in the form of a plurality of partitions for pixel formation, which is a binder resin. (A), photoactivator (B), fine particles (C) in a dispersion using an organic solvent as a dispersion medium, and the zeta potential measured by electrophoretic light scattering of the fine particles (C) in the dispersion It contains fine particles (C) of −100 to −5 mV and an organic solvent (D) that is at least partly an organic solvent of the dispersion.
The fine particles (C) are blended in the photosensitive resin composition of the present invention as a dispersion using an organic solvent as a dispersion medium (hereinafter also referred to as an organic solvent dispersion), and the zeta of the fine particles (C) in the organic solvent dispersion. The potential is −100 to −5 mV. The photosensitive resin composition of the present invention contains an organic solvent (D), and at least a part of the organic solvent (D) is an organic solvent derived from an organic solvent dispersion of fine particles (C). The photosensitive resin composition may contain an organic solvent in addition to the organic solvent derived from the fine particle (C) dispersion, and the organic solvent was blended alone in the production of the photosensitive resin composition. An organic solvent may be sufficient, and when the component in the photosensitive resin composition is mix | blended as an organic solvent solution or an organic solvent dispersion liquid, the organic solvent mix | blended with the mixing | blending of the component may be sufficient. The organic solvent (D) in this invention says the whole organic solvent contained in the photosensitive resin composition of this invention.

In the photosensitive resin composition of the present invention, the contained fine particles (C) in the specific zeta potential range attract each other with other components constituting the photosensitive resin composition while maintaining dispersibility in the composition. Acts as follows. Furthermore, since it has a strong mutual contact with a substrate, particularly a substrate having a hydroxyl group on its surface, it effectively prevents peeling of the formed partition wall from the substrate, which is likely to occur during alkali development in photolithography. Is possible. As a result, the developability by alkali development can be improved while maintaining the adhesion of the partition wall to the substrate, and a high resolution pattern can be obtained.

The photosensitive resin composition of the present invention can be a negative photosensitive resin composition as long as it is a photosensitive resin composition for forming a partition disposed on a substrate into a plurality of sections for pixel formation by photolithography. Or a positive photosensitive resin composition.
Each of these photosensitive resin compositions contains a component comprising a combination of a binder resin (A) and a photoactive agent (B), and after the organic solvent (D) is removed, the photoactive agent (B) is light. And activated by irradiation (exposure) of electron beam and acting on the binder resin (A) to change the physical properties such as solubility of the photosensitive composition.

In the photosensitive composition formed from the negative photosensitive resin composition, the photoactivator (B) activated by exposure acts on the binder resin (A) to be cured and unexposed portions (unexposed) The cured portion) is removed by development, and a pattern is formed. Depending on the type of curing, that is, the type of combination of the binder resin (A) and the photoactive agent (B), it is classified into a radical curing type, an acid curing type, and the like.
In the photosensitive composition formed from the positive photosensitive resin composition, the photoactivator (B) activated by exposure acts on the binder resin (A) to increase the solubility in the developer. The exposed portion is removed by development, and a pattern is formed. Depending on the type of the photoactive agent (B) and the binder resin (A), for example, it is classified into a type containing o-quinonediazide, a type containing a blocked acidic group, and the like.
Hereinafter, with respect to the photosensitive resin composition of the present invention, the negative photosensitive resin composition and the positive photosensitive resin composition will be described for each type.

(1) Radical curable negative photosensitive resin composition The photosensitive composition obtained by removing the organic solvent (D) from the radical curable negative photosensitive resin composition is a radical curable photosensitive composition. . This radical curable negative photosensitive resin composition that becomes a radical curable photosensitive composition is hereinafter referred to as a resin composition (NR).
Resin composition (NR) includes photo-radically polymerizable binder resin (A1) as binder resin (A), photopolymerization initiator (B1) as photoactive agent (B), fine particles (C) and organic solvent (D) is contained. As such a photo-radically polymerizable binder resin (A1) and photopolymerization initiator (B1), the photo-radically polymerizable resins used in conventionally known resin compositions (NR) for forming partition walls of optical elements are used. A combination of the binder resin (A1) and the photopolymerization initiator (B1) can be used without particular limitation.
(1-1) Binder resin (A): Photoradically polymerizable binder resin (A1)
When the negative photosensitive resin composition according to the present invention is a resin composition (NR), the binder resin (A1) contained in the resin composition (NR) has an uncured product that is alkali-soluble, and The cured product obtained by polymerization and curing is a photo-radically polymerizable binder resin (A1) that becomes insoluble in alkali. The binder resin (A1) preferably has an ethylenic double bond in order to become an alkali-insoluble cured product and has an acidic group in order to be alkali-soluble. The ethylenic double bond is polymerized by radicals generated by the photopolymerization initiator which is the photoactive agent (B), and the resin is cured by this polymerization.
The photosensitive composition containing the uncured binder resin (A1) can be removed with an alkaline developer, and the photosensitive composition containing it can be cured by curing the binder resin (A1), whereby the photosensitive composition is cured. Objects are not removed by the alkaline developer. As a result, the photosensitive film made of the photosensitive composition containing the binder resin (A1) is cured with the exposed portion and becomes alkali-insoluble, while the unexposed portion is alkali-soluble. By developing the film, the unexposed part of the film can be selectively removed.

The acidic group contained in the binder resin (A1) is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group, and two or more kinds may be used in combination.

Although it does not specifically limit as an ethylenic double bond which binder resin (A1) has, The double bond which addition polymerization groups, such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, is mentioned. More than one species may be used in combination. In addition, some or all of the hydrogen atoms of these addition polymerizable groups may be substituted with a hydrocarbon group, preferably a methyl group.

The binder resin (A1) is not particularly limited, and specific examples thereof include a resin having a side chain having an acidic group and a side chain having an ethylenic double bond. Examples of such a resin include a monomer having a reactive group such as a hydroxyl group and an epoxy group, a side chain having a reactive group obtained by copolymerizing the monomer having the acidic group, and an acidic group. And a resin (A1-1) obtained by reacting a copolymer having a side chain with a functional group capable of bonding to a reactive group and a compound having an ethylenic double bond. Other examples include a resin (A1-2) in which an ethylenic double bond and an acidic group are introduced into an epoxy resin. These may be used alone or in combination of two or more.

The monomer having a phosphoric acid group as an acidic group of the resin (A1-1) is not particularly limited, and examples thereof include 2- (meth) acryloyloxyethane phosphoric acid.

Resin (A1-2) is synthesized, for example, by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond, and then reacting with a polybasic carboxylic acid or an anhydride thereof. Can do. Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond. Next, a carboxyl group can be introduce | transduced by making polybasic carboxylic acid or its anhydride react with the epoxy resin in which the ethylenic double bond was introduce | transduced.

The epoxy resin is not particularly limited, but is bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, epoxy resin having naphthalene skeleton, Examples thereof include an epoxy resin having a biphenyl skeleton represented by the formula (1), an epoxy resin represented by the following general formula (2), and the general formula (3).

(In the formula (1), s is 1 to 50, preferably 2 to 10. The hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a substituent. (It may be substituted with an optionally substituted phenyl group.)

(In the formula (2), R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and t is 0 to 10) .)

(In Formula (3), each hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an optionally substituted phenyl group. 0 to 10)

In addition, when reacting the polybasic carboxylic acid anhydride after reacting the epoxy resin represented by the general formula (2) and the general formula (3) with a compound having a carboxyl group and an ethylenic double bond As the polybasic carboxylic acid anhydride, a mixture of dicarboxylic acid anhydride and tetracarboxylic dianhydride is preferably used. At this time, the molecular weight can be controlled by changing the ratio of the dicarboxylic anhydride and the tetracarboxylic dianhydride.

A commercially available product can be used as the resin (A1-2) in which an acidic group and an ethylenic double bond are introduced into an epoxy resin. As such commercial products, all are trade names, such as KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1163H, CCR-1166H, CCR-1159H, TCR-1025, TCR-1064H , TCR-1286H, ZAR-1535H, ZFR-1122H, ZFR-1124H, ZFR-1185H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1629H, ZAR -2001H (manufactured by Nippon Kayaku Co., Ltd.), EX1010 (manufactured by Nagase ChemteX Corporation) and the like.

As a resin (A1-2) in which an acidic group and an ethylenic double bond are introduced into an epoxy resin, an acidic group and an ethylenic double bond are introduced into an epoxy resin having a biphenyl skeleton represented by the formula (1) Resin, a resin obtained by introducing an acidic group and an ethylenic double bond into the epoxy resin represented by the formula (2), or an acid group and an ethylenic double bond introduced into the epoxy resin represented by the formula (3) Resin is preferred. When the black colorant is blended in the composition, by using the resin, a larger amount of the black colorant can be blended, and the light shielding property and optical density of the partition walls can be increased. Moreover, the film peeling of the cured portion of the photosensitive film during development is suppressed, and a high resolution pattern can be obtained. On the other hand, the linearity of the line is good and preferable. Further, a film composed of a cured portion of the photosensitive film after development is preferable because the appearance after the post-baking process is maintained and a smooth surface is easily obtained.

The binder resin (A1) used in the present invention preferably has a mass average molecular weight of 1.5 × 10 ³ to 30 × 10 ³ , more preferably 2.0 × 10 ³ to 15 × 10 ³ . When the mass average molecular weight is less than 1.5 × 10 ³ , curing during exposure may be insufficient, and when it exceeds 30 × 10 ³ , developability may be deteriorated. In the present specification, the mass average molecular weight is a value measured by gel permeation chromatography using polystyrene as a standard substance.

The number of ethylenic double bonds contained in the binder resin (A1) is preferably 3 or more, more preferably 6 or more in one molecule on average. When the number of ethylenic double bonds is 3 or more, the difference in alkali solubility between the exposed portion and the unexposed portion is likely to be different, and a fine pattern can be formed with a smaller exposure amount.

The binder resin (A1) preferably has an acid value of 10 to 300 mgKOH / g, more preferably 30 to 150 mgKOH / g. When it is 10 to 300 mgKOH / g, the developability of the photosensitive composition is good. In addition, an acid value means the milligram number of potassium hydroxide required in order to neutralize the resin acid etc. in 1g of samples.

The content of the binder resin (A1) in the resin composition (NR) according to the present invention is preferably 5 to 80% by mass and more preferably 10 to 60% by mass with respect to the total solid content of the composition. preferable. When the content is 5 to 80% by mass, the developability of the photosensitive composition is good.

(1-2) Photoactivator (B): Photopolymerization initiator The photopolymerization initiator (B1), which is the photoactivator (B) contained in the resin composition (NR), may be an ordinary radical curable type photosensitivity. The photopolymerization initiator used for the resin composition can be used without any particular limitation.
The photopolymerization initiator (B1) is not particularly limited as long as it is a compound that generates radicals upon irradiation with light. Specific examples include benzyl, diacetyl, methylphenylglyoxylate, 9,10-phenanthrene. Α-diketones such as quinone; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone Thioxanthones such as isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, thioxanthone-4-sulfonic acid; benzophenone, 4,4′-bis (dimethyl) Benzophenones such as (lamino) benzophenone and 4,4′-bis (diethylamino) benzophenone; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2 -Phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane Acetophenones such as -1-one; quinones such as anthraquinone, 2-ethylanthraquinone, camphorquinone, 1,4-naphthoquinone; ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Acid (n-bu Toxi) ethyl, isoamyl 4-dimethylaminobenzoate, aminobenzoic acid such as 4-dimethylaminobenzoic acid 2-ethylhexyl; halogen compounds such as phenacyl chloride, trihalomethylphenylsulfone; acylphosphine oxides; di-t-butyl Peroxides such as peroxides; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazoyl-3-yl] -1- (O-acetyloxime) and the like, and two or more of them may be used in combination.

Among these, the photopolymerization initiator (B1) used in the present invention is preferably a compound represented by the following general formula (4).

(In the formula (4), R ²¹ is substituted with a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group. An unsubstituted phenyl group having 6 to 20 carbon atoms or an alkyl group substituted or unsubstituted phenoxy group having 6 to 20 carbon atoms, R ²² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 8 carbon atoms, a phenyl group substituted or substituted with an alkyl group having 6 to 20 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, and an alkyl group substituted or unsubstituted with 7 carbon atoms benzoyl-20, a phenoxycarbonyl group alkoxycarbonyl group or an alkyl group substituted or unsubstituted 7 to 20 carbon atoms having a carbon number of 2 - 12, R ²³ is the number of 1 to 12 carbon atoms A le ^{^{^{radical, R 24, R 25, R}}} 26 and ^{R 27} each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, the carbon number of the substituted or unsubstituted alkyl group of 3-8 A cyclohexyl group, an alkyl group substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, an alkyl group substituted or unsubstituted benzoyl group having 7 to 20 carbon atoms, alkyl Substituted or unsubstituted benzylcarbonyl group having 7 to 20 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, substituted or unsubstituted phenoxycarbonyl group having 7 to 20 carbon atoms, carbon number Is an amide group or nitro group of 1 to 20)

In the compound represented by the general formula (4), R ²¹ is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group having 6 to 12 carbon atoms substituted or unsubstituted with an alkyl group, such as a methyl group, Examples include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a phenyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is particularly preferable.

In the compound represented by the general formula (4), R ²² is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group having 2 to 5 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group and the like. Among them, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.

In the compound represented by the general formula (4), examples of the alkyl group having 1 to 12 carbon atoms represented by R ²³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like. Among these, an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 2 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

In the compound represented by the general formula (4), R ²⁴ , R ²⁶ and R ²⁷ are preferably hydrogen atoms.

In the compound represented by the general formula (4), R ²⁵ is a benzoyl group substituted or unsubstituted with an alkyl group having 7 to 20 carbon atoms or an alkyl group substituted or unsubstituted with 7 to 20 carbon atoms. A benzylcarbonyl group is preferable, and a 2-methylbenzoyl group, a benzylcarbonyl group, or a 1,3,5-trimethylbenzylcarbonyl group is particularly preferable.

The compound represented by the general formula (4) (O-acyloxime compound) is not particularly limited, but in the general formula (4), R ²¹ is a phenyl group, R ²² is an octyl group, and R ²³ is an ethyl group. R ²⁴ , R ²⁶ and R ²⁷ are hydrogen atoms, R ²⁵ is a benzoyl group; R ²¹ is a methyl group, R ²² is a butyl group, heptyl group or octyl group, R ²³ is an ethyl group, R ²⁴ , R ²⁶ and R ²⁷ are hydrogen atoms and R ²⁵ is a benzoyl group; R ²¹ is a phenyl group, R ²² is an octyl group, R ²³ is an ethyl group, R ²⁴ , R ²⁶ and R ²⁷ are hydrogen atoms, and R ²⁵ is compound 2-methylbenzoyl ^{group; R 21} is a methyl ^{group, R 22} is a methyl group or an octyl ^{group, R 23} is ^{^ethyl, R} ^24, R ²⁶ and ^{R 27} are hydrogen atoms, R ⁵ is a 2-methylbenzoyl group ^{compound; R 21} and ^{R 22} is a methyl ^{group, R 23} is ^{^ethyl, R} ^24, R ²⁶ and ^{R 27} are hydrogen ^{atoms, R 25} is 2-methyl-5-tetrahydrofuranyl-methoxy Examples thereof include compounds that are a benzoyl group, a 2-methyl-4-tetrahydropyranylmethoxybenzoyl group, or a 2-methyl-5-tetrahydropyranylmethoxybenzoyl group.

A commercially available product can be used as the photopolymerization initiator (B1). Examples of commercially available products include OXE02 (trade name, manufactured by Ciba Specialty Chemicals, Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl) Oxime): a compound in which R ²¹ and R ²² are methyl groups, R ²³ is an ethyl group, R ²⁴ , R ²⁶ and R ²⁷ are hydrogen atoms, and R ²⁵ is a 2-methylbenzoyl group in the above general formula (4)) IRGACURE OXE01 (trade name, manufactured by BASF, corresponding to 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)]), Adekaoptomer N-1919, Adeka Acruz NCI-831, Adeka Arcles NCI-930 (manufactured by ADEKA) and the like.

The blending ratio of the photopolymerization initiator (B1) in the resin composition (NR) according to the present invention depends on the type and use of the optical element to be used, but with respect to the photoradical polymerizable binder resin (A1). The content is preferably 1 to 50% by mass, and more preferably 5 to 25% by mass. Within such a range, the curability and developability of the photosensitive composition will be good.

Further, the content of the photopolymerization initiator (B1) in the total solid content of the resin composition (NR) according to the present invention is preferably 1 to 40% by mass, and more preferably 2 to 20% by mass. Within this range, the curability of the photosensitive composition is good, and a pattern or line width close to the mask pattern can be formed by exposure and development.

Along with the photopolymerization initiator (B1), 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 1,4-butanol bis (3-mercaptobutyrate), tris (2-mercaptopropanoyl) When a thiol compound such as (oxyethyl) isocyanurate or pentaerythritol tetrakis (3-mercaptobutyrate) is used, a sensitizing effect may be exhibited.

(1-3) Fine particles (C)
The resin composition (NR) according to the present invention contains, as an essential component, fine particles (C) whose zeta potential measured by the electrophoretic light scattering method of the fine particles (C) in the dispersion is −100 to −5 mV. The following description regarding the fine particles (C) is common not only to the resin composition (NR) but also to all the photosensitive resin compositions of the present invention, unless otherwise specified in the present specification.
As the fine particles (C), various inorganic fine particles and organic fine particles whose zeta potential measured by an electrophoretic light scattering method described below is −100 to −5 mV can be used. The zeta potential of the fine particles (C) is preferably −80 to −8 mV, more preferably −50 to −10 mV, and particularly preferably −35 to −12 mV.

<Method for measuring zeta potential>
For the zeta potential, a sample prepared by adjusting a dispersion in which fine particles (C) are dispersed in a dispersion medium so that the ratio of the fine particles (C) to the total amount of the dispersion is 6.0 × 10 ⁻⁴ mass% is manufactured by Otsuka Electronics Co., Ltd. , Measured with ELSZseries of zeta potential measurement system. Note that the measured value is a value obtained by calculating the zeta potential (ζ) from the following Huckel equation based on the physical property values (refractive index, viscosity, and relative dielectric constant) of the dispersion medium used in the sample preparation. The sample for measurement may be prepared as described above using the same dispersion medium used for the dispersion. When preparing a measurement sample from a single particle (C), a dispersion medium capable of sufficiently dispersing the particle (C) is selected according to the surface state of the particle, for example, the hydroxyl group concentration of the particle (C). Then, a dispersion liquid having the above concentration is prepared as a measurement sample.

(In the formula, ε ₀ , ε _r , and η respectively represent the dielectric constant, relative dielectric constant, and viscosity (mPa · s) of the dispersion medium at 25 ° C. ζ (mV) is the zeta potential.)

In this specification, the zeta potential of the fine particles (C) refers to the zeta potential measured by the above method. In the photosensitive resin composition of the present invention, a dispersion of fine particles (C) is blended, and the zeta potential of the fine particles (C) in the blended dispersion is −100 to −5 mV.
The photosensitive resin composition in the present invention constitutes the photosensitive resin composition while the fine particles (C) are dispersed in the composition by the fine particles (C) contained therein being the fine particles in the dispersion. It acts so as to attract other components to each other, and further has a strong mutual adhesion action with a substrate, particularly a substrate having a hydroxyl group on the surface, so that the formed partition wall has high adhesion at the substrate interface. Retained and difficult to peel off during development. As a result, a high resolution pattern can be obtained. The fine particles (C) have excellent dispersibility in the photosensitive resin composition, and therefore the photosensitive resin composition in the present invention exhibits excellent storage stability.

Furthermore, in the photosensitive resin composition of the present invention, when the partition is formed by photolithography using the photosensitive resin composition by containing the fine particles (C), a post-baking step performed after development is performed. The effect of improving the shape stability of the pattern against heating can also be obtained.

The fine particles (C) are preferably transparent fine particles from the viewpoint of exposure as characteristics other than the zeta potential. Further, the average particle diameter of the fine particles (C) by the laser diffraction scattering method is preferably 5 to 100 nm, more preferably 10 to 80 nm, and more preferably 20 to 50 nm from the viewpoints of adhesion to development and surface smoothness of the formed partition wall. Is particularly preferred.

In addition, the fine particles (C) preferably do not absorb the wavelength of light irradiated in the exposure step in order not to lower the sensitivity of the photosensitive composition, and in particular i which is the main emission wavelength of an ultrahigh pressure mercury lamp. More preferable are those that do not absorb the line (365 nm), h line (405 nm), and g line (436 nm).

Among the fine particles (C), examples of the inorganic fine particles include fine particles of silica, zirconia, magnesium fluoride, ITO (indium tin oxide), ATO (antimony tin oxide), and the like. Examples of the organic fine particles include fine particles such as polyethylene and PMMA. From the viewpoint of heat resistance, the fine particles (C) used in the present invention are preferably inorganic fine particles, more preferably silica fine particles and zirconia fine particles from the viewpoint of dispersion stability, and particularly preferably silica fine particles from the viewpoint of availability.

In the photosensitive resin composition of the present invention, the fine particles (C) are contained in a dispersed state in the photosensitive resin composition. Here, the “dispersed state” specifically refers to a state of being dispersed by electrostatic interaction (repulsive force). The photosensitive resin composition of the present invention is a composition in which a dispersion of fine particles (C) is blended, and the zeta potential of the fine particles (C) in the dispersion is −100 to −5 mV. By blending the fine particles (C) having such characteristics, the fine particles (C) do not settle or aggregate in the photosensitive resin composition, and are dispersed in the photosensitive resin composition in a stable state. It is possible.
Specifically, the dispersion medium in such a dispersion of fine particles (C) is selected from organic solvents having an SP value of 9 to 20 (cal / cm ³ ) ^1/2 having at least one hydroxyl group. A seed | species or 2 or more types is mentioned. The SP value of such a dispersion medium is preferably 9 to 18 (cal / cm ³ ) ^{1/2, and} more preferably 10 to 15 (cal / cm ³ ) ^1/2 .

Here, the SP value (solubility parameter) of a solvent is the aggregation energy density of the solvent, that is, a value obtained by multiplying the evaporation energy per unit volume of one molecule by 1/2 power, and the magnitude of the polarity per unit volume. It is a numerical value shown. The unit is (cal / cm ³ ) ^1/2 and refers to the value at 25 ° C. in this specification unless otherwise specified. The SP value can be calculated by the Fedros method (see: RF Fedros, Polym. Eng. Sci., 14 [2] 147 (1974)).
Specific examples of such an organic solvent include organic solvents shown in Table 1 below. Examples of the organic solvent include alkanols having 4 or less carbon atoms, alkylene glycols having 2 or 3 carbon atoms and dimers thereof, and monoalkyl ethers of the alkylene glycol and dimers thereof (the alkyl ether portion has 4 or less carbon atoms). Is particularly preferred.

Further, the organic solvent used as the dispersion medium of the fine particles (C) may be a mixture of two or more of these, and the SP value of the mixed solvent is in the range of 9 to 20 (cal / cm ³ ) ^1/2. It may be a mixture with other solvents. Of these, methanol, 2-propanol, and ethylene glycol monopropyl ether are preferable. When silica fine particles are used as the fine particles (C), 2-propanol and ethylene glycol monopropyl ether are particularly preferable.

Colloidal silica is preferable as the fine particles (C). Examples of the colloidal silica in which the silica fine particles have a zeta potential of −100 to −5 mV in the organic solvent dispersion include organosilica sols using the organic solvent as a dispersion medium.

As such an organosilica sol, a commercially available product can be used. As a commercially available product, for example, NPCST (trade name, manufactured by Nissan Chemical Industries, zeta potential: −15 mV, average particle size: 24 nm, dispersion medium: Ethylene glycol monopropyl ether, solid content: 30% by mass), IPAST (trade name, manufactured by Nissan Chemical Industries, zeta potential: -28 mV, average particle size: 45 nm, dispersion medium: 2-propanol, solid content: 30% by mass And the like.

The content ratio of the fine particles (C) in the total solid content of the photosensitive resin composition of the present invention is preferably 3 to 35 mass%, preferably 5 to 30 mass%, where the total solid content of the photosensitive resin composition is 100 mass%. % Is more preferable, 7 to 25% by mass is further preferable, and 10 to 23% by mass is particularly preferable. When the content is too small, the effect of suppressing the peeling of the formed resin patterning layer during alkali development is small, and when the content is too large, the stability of the liquid of the composition tends to decrease.

Moreover, the compounding of the fine particles (C) into the photosensitive resin composition has an effect of improving the shape stability of the pattern against heating in the post-baking process. Although it depends on the kind of the binder resin (A) and the heating conditions, the blending amount of the fine particles (C) for obtaining sufficient pattern shape stability is 100 mass of the total solid content of the photosensitive resin composition. % Is preferably 12 to 30% by mass, more preferably 15 to 25% by mass, and particularly preferably 18 to 23% by mass.

(1-4) Organic solvent (D)
The photosensitive resin composition of the present invention contains an organic solvent (D). At least a part of the organic solvent (D) is a dispersion medium for the dispersion liquid of the fine particles (C). In addition, the following description regarding this organic solvent (D) is common not only to the resin composition (NR) but all the photosensitive resin compositions of this invention unless there is particular notice in this specification.
As a part of the organic solvent (D), an organic solvent different from the dispersion medium of the dispersion liquid of the fine particles (C) may be contained. The organic solvent may be the same organic solvent as the dispersion medium or a different organic solvent. For example, when the solid content concentration of the photosensitive resin composition is too high just by adding the dispersion liquid of fine particles (C), the solid content concentration is set to a predetermined value by using the same or different organic solvent as the dispersion medium of the dispersion liquid. The concentration can be adjusted. Further, after adjusting the concentration of the fine particles (C) of the dispersion using the same or different organic solvent as the dispersion medium, the solid content concentration of the photosensitive resin composition is similarly adjusted by using the dispersion. Can also be done.

When an organic solvent different from the dispersion medium of the dispersion is used, the organic solvent (D) in the photosensitive resin composition becomes a mixture of the organic solvent of the dispersion medium and another organic solvent. The dispersion stability of the fine particles (C) dispersed in the organic solvent (D) in the product may be lowered. Therefore, when using an organic solvent that is different from the dispersion medium, use an organic solvent that has similar characteristics (dielectric constant, relative dielectric constant, viscosity, etc.) to the organic solvent of the dispersion medium so that the change in zeta potential is reduced. It is preferable to use an organic solvent that causes little decrease in dispersion stability, for example, by reducing the amount of the organic solvent that is different from the dispersion medium.
As the organic solvent used separately from the dispersion medium, the organic solvents mentioned as the dispersion medium are preferable. In particular, an organic solvent having at least one hydroxyl group and having an SP value of 9 to 20 (cal / cm ³ ) ^1/2 that is the same as or different from the dispersion medium in the dispersion to be used is preferable.

As the organic solvent (D), in addition to those blended as a dispersion medium in the photosensitive resin composition and those blended alone separately, those blended with other components may be blended. Good. For example, when the photoactive agent (B) is blended as a solution, a colorant (E) described later is blended as a dispersion, an ink repellent agent described later is blended as a solution, and the like. . As an organic solvent mix | blended with the mixing | blending of another component, when the compounding quantity is small, the kind is not specifically limited. However, when the amount of the dispersion medium is relatively large in comparison with the total amount of what is blended separately from that, it is preferably an organic solvent of the type mentioned as the dispersion medium, It is preferable that the organic solvent is the same as the dispersion medium to be used or the same organic solvent as that added separately from the dispersion medium.
The total amount of the organic solvent (D) is preferably adjusted so that the solid concentration in the photosensitive resin composition is 5 to 40% by mass, and is adjusted to be 10 to 25% by mass. Is more preferable.

(1-5) Optional component In addition to the essential components (A) to (C), the resin composition (NR) according to the present invention includes, as appropriate, the colorant (E), Ink repellent agent, radical crosslinking agent or thermal crosslinking agent that increases the crosslink density of the cured product, silane coupling agent to obtain substrate adhesion, phosphoric acid compound, surfactant, curing accelerator, thickener, plastic An agent, an antifoaming agent, a leveling agent, a repellency inhibitor, an ultraviolet absorber, a solvent, and the like can be blended.

(Colorant (E))
In the photosensitive resin composition of the present invention, the effect of the present invention becomes more remarkable when the partition is a light-shielding layer having a light-shielding property, that is, when used as a black matrix. Therefore, the photosensitive resin composition of the present invention is preferably applied to the production of an optical element whose partition is a light shielding layer.

When the partition formed from the resin composition (NR) according to the present invention is used as a black matrix in this way, it is preferable that the photosensitive resin composition contains a black colorant. Specific examples of such a black colorant include carbon black, aniline black, anthraquinone black pigment, metal oxide particles such as titanium black, black metal oxide pigment, alloy particles such as silver tin alloy, and perylene. Black pigments such as C.I. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned.

As the black colorant, organic pigments such as red pigments, blue pigments, green pigments and yellow pigments, and mixtures of azomethine black pigments and inorganic pigments can also be used. Further, the black colorant is preferably carbon black from the viewpoint of cost and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together. For black matrix on array type color filters and organic EL elements, low dielectric constant and high resistance films and partition walls are required. In order to obtain the film or partition, it is preferable to use a mixture of the above organic pigments and an azomethine black pigment.

The amount of the black colorant depends on the type and use of the optical element to be used. For example, when a partition is used as the black matrix of the color filter, the total solid content of the photosensitive resin composition is used. It is preferable that 10 to 50% by mass of a black colorant is prepared and blended as a dispersion together with an appropriate dispersion medium and dispersant as necessary. The photosensitive resin composition obtained when the blending amount of the black colorant is within the above range has good sensitivity, and the formed partition has excellent light shielding properties.

(Ink repellent)
In the photosensitive resin composition of the present invention, partition walls are formed by photolithography using the photosensitive resin composition, whereby the substrate is partitioned into a plurality of sections, and pixel formation regions of optical elements (hereinafter referred to as “dots”). May be formed). Here, when this partition is used as a partition of an optical element in which pixels are formed by an inkjet method, the photosensitive resin composition of the present invention imparts ink repellency to the upper surface of the resulting partition. It is preferable to contain an ink repellent agent. Here, the ink repellency means water repellency or oil repellency, or both water repellency and oil repellency, depending on the composition of the ink. More specifically, it refers to the property of repelling solvents such as water and organic solvents used in inks, and generally water and appropriate organic solvents such as 1-methoxy-2-acetoxypropane and propylene glycol, respectively. It can be evaluated by a contact angle of an organic solvent contained in an ink used in a normal ink jet method such as 1-monomethyl ether 2-acetate (PGMEA).

The ink repellent agent used in the photosensitive resin composition of the present invention is used for the required ink repellency, that is, ink, on the upper surface of the partition when the photosensitive resin composition containing it forms the partition. It is a compound capable of imparting properties to repel solvents such as water and organic solvents.

As the ink repellent agent that imparts ink repellency to the upper surface of the partition when the partition is formed by blending with such a photosensitive resin composition, preferably a fluorine-containing compound, silicon-containing compound, fluorine atom And compounds having both a silicon atom and the like.

Examples of the fluorine-containing compound used as the ink repellent agent include conventionally known fluorine-containing compounds for ink repellent agents such as fluoroolefin resins and polymers having a fluoroalkyl group in the side chain.

Further, examples of the silicon-containing compound used as the ink repellent agent include conventionally known silicon-containing compounds for ink repellent agents, such as polymers having a dimethylsiloxane group, without any particular limitation.

As the compound having both fluorine atom and silicon atom used as the ink repellent agent, conventionally known fluorine-containing silicon compound for ink repellent agent, for example, fluorine-containing silane coupling agent, having both a fluoroalkyl group and a dimethylsiloxane group A polymer etc. are mentioned without a restriction | limiting in particular.

Among such ink repellent agents, a polymer having a fluoroalkyl group in the side chain can be mentioned as a preferred embodiment because of its high ability to impart ink repellency. Such a polymer having a fluoroalkyl group in the side chain can be produced by a conventionally known method, for example, a method disclosed in JP-A Nos. 2000-102727 and 2002-249706.
The ink repellent agent described above can be used regardless of the type of the photosensitive resin composition unless otherwise specified in the present specification.

Furthermore, as a preferred embodiment of the ink repellent agent in the case of the resin composition (NR), a polymer having a fluoroalkyl group and an ethylenic double bond in the side chain can be mentioned. The reason for this is that if the polymer having a fluoroalkyl group and an ethylenic double bond in the side chain is used as the ink repellent agent, the ink repellent agent is used in the exposure step and post-bake step for forming a partition wall by photolithography, which will be described later. It reacts with the other compounding components in the negative photosensitive resin composition and is to be immobilized on the partition upper surface.

As a preferred embodiment of the polymer having such a fluoroalkyl group and an ethylenic double bond in the side chain, a straight chain having 20 or less carbon atoms in which at least one of the hydrogen atoms, preferably all of them are substituted with fluorine atoms, is used. Polymer units having a chain-like or branched alkyl group (wherein the alkyl group includes those having etheric oxygen), and ethylenic divalent groups such as (meth) acryloyl group, allyl group, vinyl group, vinyl ether group, etc. A polymer containing a polymer unit having a heavy bond can be exemplified.

The number average molecular weight of the polymer having a fluoroalkyl group and an ethylenic double bond in the side chain, preferably used as the ink repellent agent, is preferably from 500 to 150,000, more preferably from 1,000 to 100,000. The mass average molecular weight is preferably 1,000 to 300,000, more preferably 5,000 to 150,000. Within this range, alkali solubility and developability are good. The fluorine content in the polymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 12 to 30% by mass from the viewpoints of ink repellency and partition wall moldability. %. Further, the number of ethylenic double bonds in the side chain of this polymer is preferably 0.5 to 5.0 mol / g, more preferably 1.0 to 3.0 mol / g. Within this range, developability is good.

Furthermore, the polymer can have a silicone chain (straight chain) having about 200 or less silicon in the side chain. The silicon content in the polymer is preferably 0.5 to 30% by mass, more preferably 0.5 to 10% by mass from the viewpoints of ink repellency and partition wall moldability.

Here, the polymer used as the ink repellent agent preferably has at least one acidic group selected from the group consisting of an acidic group, for example, a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. The reason for this is that it has alkali solubility, so that the ink repellent agent hardly remains in the region (dot) partitioned by the partition on the substrate, and the ink spreads well when the ink is injected by the ink jet method. Because it becomes. From such a viewpoint, the acid value of the polymer is preferably 5 to 200 mgKOH / g, more preferably 10 to 100 mgKOH / g, and particularly preferably 20 to 60 mgKOH / g.

The above-described polymer having a fluoroalkyl group, an ethylenic double bond, and optionally a silicone chain in the side chain, preferably further having an acidic group, is a conventionally known method, specifically, International Publication No. WO 2004/2004. / 042474, International Publication No. 2007/069703, International Publication No. 2008/149976, and the like.

The content ratio of the ink repellent agent in the solid content of the resin composition (NR) containing the ink repellent agent is preferably in the range of 0.01 to 30% by mass with respect to the total amount of the solid content of the composition. The reason is that the obtained partition walls have good ink repellency, good wet spread in the dots of ink injected by the ink jet method, and good uniformity of the injected ink layer.

The polymer containing fluorine atoms and / or silicon atoms to be blended in the photosensitive resin composition as the ink repellent agent usually also has an action as a surfactant. Therefore, when the photosensitive resin composition contains an ink repellent agent, a surfactant is not further blended unless particularly required to be added. A photosensitive resin composition for forming a partition for an optical element that performs pixel formation by a method other than the inkjet method usually does not contain an ink repellent, and therefore, it is preferable to add a surfactant. As the surfactant, the same polymer as the ink repellent agent may be used, but a commercially available product may be used.

Examples of such surfactants include silicone surfactants and acrylic surfactants. Specific examples of commercially available products include BYK-306 (trade name, manufactured by Big Chemie Japan, 12% by mass solution of polyether-modified polydimethylsiloxane (xylene / monophenyl glycol (7/2)), BYK-323 ( Trade name, manufactured by Big Chemie Japan, Aralkyl-modified polymethylalkylsiloxane), BYK-320 (trade name, manufactured by Big Chemie Japan, 52% solution of polyether-modified polymethylalkylsiloxane (White Spirit / PGMEA (9/1) )), BYK-350 (trade name, manufactured by BYK Japan, Inc., acrylic copolymer).
The blending amount of the surfactant is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass with respect to the total solid content of the photosensitive resin composition, although it depends on the type of surfactant used. More preferred.

(Radical crosslinking agent)
The resin composition (NR) according to the present invention preferably contains a radical crosslinking agent, specifically a radical crosslinking agent having two or more ethylenic double bonds, as an optional component for promoting radical curing. Thereby, the sclerosis | hardenability of the said binder resin (A1) at the time of exposure improves, and the exposure amount at the time of forming a partition can be reduced. In addition, it is preferable that the radical crosslinking agent used for this invention does not have an acidic group substantially.

The radical crosslinking agent having two or more ethylenic double bonds is not particularly limited, but diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, ethoxylated isocyanuric acid triacrylate, urethane acrylate and the like. These may be used alone or in combination of two or more.

In the present invention, it is possible to use a commercially available product as a radical crosslinking agent having two or more ethylenic double bonds. As such commercially available products, KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ester A-9300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) Ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name) Manufactured by Maruzen Petrochemical Co., Ltd., bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane), BANI-X (trade name, Maruzen Petrochemical) N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5 Down-2,3-dicarboximide)), and the like.

Examples of urethane acrylate include KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D. -P20 and the like. A-9300, BANI-M and BANI-X are preferable from the viewpoint of imparting hardness to the cured product and suppressing thermal sagging. A-9300-1CL is preferable from the viewpoint of imparting flexibility to the cured product. Urethane acrylate is preferable because an appropriate development time can be realized and developability is improved.

The content of the radical crosslinking agent in the resin composition (NR) according to the present invention is preferably 1 to 50% by mass and more preferably 5 to 30% by mass with respect to the total solid content of the composition. When the content is 1 to 50% by mass, the developability of the photosensitive resin composition is improved.

(Thermal crosslinking agent)
The thermal crosslinking agent is a compound having two or more groups capable of reacting with the functional group of the binder resin (A1) contained in the added photosensitive resin composition, and is subjected to heat treatment, specifically after development. It is an optional component that improves heat resistance by reacting with the binder resin (A1) by heat treatment by post-baking or the like and increasing the cross-linking density of the cured product.

The thermal crosslinking agent depends on the type of the crosslinking reactive functional group of the binder resin (A1) to be crosslinked and cured. Depending on the type, for example, an amino resin, a compound having two or more epoxy groups, 2 Compounds having one or more hydrazino groups, polycarbodiimide compounds, compounds having two or more oxazoline groups, compounds having two or more aziridine groups, polyvalent metals, compounds having two or more mercapto groups, polyisocyanates Compounds and the like. These may be used alone or in combination of two or more.

Among these, as the thermal crosslinking agent added to the resin composition (NR) in the present invention, an amino resin and a compound having two or more epoxy groups are preferable from the viewpoint of solvent resistance, and two or more epoxy groups are preferable. Particularly preferred are compounds having

Specific examples of compounds having two or more epoxy groups include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, trisphenol methane type epoxy resins, and brominated epoxy resins. Glycidyl ethers such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, alicyclic epoxy resins such as bis (2,3-epoxycyclopentyl) ether, diglycidyl hexahydrophthalate, diglycidyl tetrahydro Glycidyl esters such as phthalate and diglycidyl phthalate, glycidyl amines such as tetraglycidyl diaminodiphenylmethane and triglycidyl paraaminophenol, triglycidyl iso Heterocyclic epoxy resins such as cyanurate and the like.

In addition, an epoxy resin having a biphenyl skeleton represented by the above general formula (1) (for example, a commercial product such as NC-3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd.)), represented by the general formula (2) An epoxy resin represented by the general formula (3) can also be used as a thermal crosslinking agent.

Amino resins include compounds in which some or all of the amino groups such as melamine compounds, guanamine compounds, and urea compounds are hydroxymethylated, or some or all of the hydroxyl groups of the hydroxymethylated compounds are methanol, ethanol And compounds etherified with n-butyl alcohol, 2-methyl-1-propanol, and the like. Specifically, hexamethylol melamine and alkylated hexamethylol melamine (such as hexamethoxymethyl melamine), hexabutyrol melamine, partially methylolated melamine and its alkylated product, tetramethylol benzoguanamine and alkylated tetramethylol benzoguanamine; partially methylolated benzoguanamine And alkylated products thereof; and the like.

The blending ratio of the thermal crosslinking agent in the resin composition (NR) according to the present invention is 1 to 50% by mass with respect to the total solid content of the composition, although it depends on the type and use of the optical element used. It is preferably 5 to 30% by mass. Within such a range, the crosslink density of the cured product constituting the partition obtained by using this increases, and a partition having excellent heat resistance can be obtained.

(Silane coupling agent)
The resin composition (NR) according to the present invention may contain a silane coupling agent as an optional component. By blending a silane coupling agent, the adhesion of the resulting partition to the substrate is further improved, which is preferable.

Specific examples of such silane coupling agents include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-chloro. Examples thereof include propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane and the like. These may be used alone or in combination of two or more.

In the resin composition (NR) according to the present invention, the ratio of the silane coupling agent in the total solid content is preferably 0.1 to 20% by mass, and more preferably 1 to 10% by mass. If the content is too small, the effect of improving the adhesion of the partition walls formed from the resulting photosensitive resin composition to the substrate is small, and if the content is too large, a residue may be easily generated after development, which is not preferable. .

(Phosphate compound)
The resin composition (NR) may contain a phosphoric acid compound as necessary. Adhesiveness with a board | substrate can be improved because a resin composition (NR) contains a phosphoric acid compound. Examples of the phosphoric acid compound (L) include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.

In the resin composition (NR) according to the present invention, the composition ratio of the total solid content is as follows: photoradical polymerizable binder resin (A1): photopolymerization initiator (B1): fine particles (C) = 5 to 80% by mass : 1 to 40% by mass: preferably 3 to 35% by mass.
The more preferable composition ratio of the total solid content of the resin composition (NR) according to the present invention is: radical photopolymerizable binder resin (A1): photopolymerization initiator (B1): fine particles (C): colorant (E ): Optional components other than the colorant (E) = 5 to 80% by mass: 1 to 40% by mass: 3 to 35% by mass: 10 to 50% by mass: 2.2 to 50% by mass.

The resin composition (NR) according to the present invention is prepared by uniformly mixing the above-described various essential components and optional components added as necessary according to the above-mentioned blending amount by a normal method. be able to.

(2) Acid-curable resin composition The photosensitive composition obtained by removing the organic solvent (D) from the acid-curable negative photosensitive resin composition is an acid-curable photosensitive composition. This acid-curable negative photosensitive resin composition that becomes an acid-curable photosensitive composition is hereinafter referred to as a resin composition (NA).
When the photosensitive resin composition of the present invention is a resin composition (NA), the photosensitive resin composition includes an alkali-soluble resin (A21) having a carboxyl group and / or a phenolic hydroxyl group as the binder resin (A), A crosslinkable resin (A22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group, a photoacid generator (B2) as a photoactive agent (B), and an organic solvent dispersion The fine particles (C) having a zeta potential of −100 to −5 mV measured by the electrophoretic light scattering method of the fine particles (C) in the dispersion, and the organic solvent (D) as essential components Contained as.

Resin composition (NA) comprises an alkali-soluble resin (A21) having a carboxyl group and / or a phenolic hydroxyl group, wherein an acid is generated from the photoacid generator (B2) in the light-irradiated part upon exposure in photolithography, etc. A cured product of the photosensitive composition is formed by a crosslinking reaction with the crosslinkable resin (A22), which is a compound having two or more groups capable of reacting with a group and / or a phenolic hydroxyl group. It is preferable that the part not exposed to light (unexposed part) is soluble in a developer used for the development performed after the exposure, usually an alkali developer.

Here, for the fine particles (C) and the organic solvent (D), which are essential components contained in the resin composition (NA) according to the present invention, the above (1) resin composition ( NR). Hereinafter, the essential components other than the fine particles (C) and the organic solvent (D) and the optional components will be described in this order.

(2-1) Binder resin (A): alkali-soluble resin (A21) / crosslinkable resin (A22)
When the photosensitive resin composition of the present invention is a resin composition (NA), the binder resin (A) is subjected to a crosslinking reaction by the action of an acid generated by a photoacid generator (B2) as a photoactive agent (B). A combination of an alkali-soluble resin (A21) having a carboxyl group and / or a phenolic hydroxyl group and a crosslinkable resin (A22) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group. Can be mentioned.

(Alkali-soluble resin (A21))
The alkali-soluble resin (A21) has a carboxyl group and / or a phenolic hydroxyl group. A crosslinkable resin (A22) which is a compound which is soluble in an alkaline solution by having a carboxyl group and / or a phenolic hydroxyl group and which has two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group; It can crosslink and form a cured product of the photosensitive composition. The alkali-soluble resin (A21) can be used without any limitation as long as it is a resin that is soluble in an alkaline solution constituting a developer used in photolithography of the photosensitive composition. And a resin (A21-1) obtained by polymerizing a monomer having an ethylenic double bond and / or a monomer having a phenolic hydroxyl group and an ethylenic double bond, a phenol resin, and the like. .

Resin (A21-1) obtained by polymerizing a monomer having a carboxyl group and an ethylenic double bond and / or a monomer having a phenolic hydroxyl group and an ethylenic double bond as an essential component has It can be obtained by copolymerizing a monomer having an ionic double bond and / or a monomer having a phenolic hydroxyl group and an ethylenic double bond, if necessary, with another monomer. In the alkali-soluble resin (A21-1), the proportion of monomer units based on other monomers is preferably 30 to 95% by mass, more preferably 50 to 90% by mass. Within this range, the alkali solubility and developability of the photosensitive composition are good.

The monomer having a carboxyl group and an ethylenic double bond used for producing the alkali-soluble resin (A21-1) includes acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid. Examples include acids, fumaric acid, cinnamic acid, or salts thereof. Examples of the monomer having a phenolic hydroxyl group and an ethylenic double bond include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and the like, in which one or more hydrogen atoms of these benzene rings are methyl, ethyl, Alkyl groups such as n-butyl, alkoxy groups such as methoxy, ethoxy and n-butoxy, halogen atoms, haloalkyl groups in which one or more hydrogen atoms of the alkyl group are substituted with halogen atoms, nitro groups, cyano groups, amide groups And the like.

Examples of other monomers include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic acid esters, (meth) acrylamides, Aromatic vinyl compounds, chloroolefins, conjugated dienes and the like can be mentioned, and considering the heat resistance of the partition wall, (meth) acrylic acid esters or (meth) acrylamides are preferable. Note that these compounds may have a functional group such as a carbonyl group or an alkoxy group.

Examples of the phenol resin include aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol and hydroquinone and phenols which are at least one selected from these alkyl-substituted or halogen-substituted aromatic compounds as aldehydes such as formaldehyde, acetaldehyde and benzaldehyde. For example, a phenol / formaldehyde resin, a cresol / formaldehyde resin, or a phenol / cresol / formaldehyde cocondensation resin can be used.

Commercial products can be used as the alkali-soluble resin (A21). As such a commercially available product, for example, EP4020G (trade name, Asahi Organic Materials Co., Ltd.) is used as a cresol novolak resin which is one of novolak-type phenol resins obtained by condensing phenols and aldehydes in the presence of an acidic catalyst. Kogyo Co., Ltd.), CRG-951 (trade name, manufactured by Showa Polymer Co., Ltd.) or polyhydroxystyrene.

The acid value of the alkali-soluble resin (A21) is preferably 10 to 600 mgKOH / g, more preferably 50 to 300 mgKOH / g. Within this range, the developability of the photosensitive resin composition will be good.

The number average molecular weight of the alkali-soluble resin (A21) is preferably 200 to 20,000, and more preferably 2,000 to 15,000. Within this range, the alkali solubility and developability of the photosensitive resin composition will be good. The mass average molecular weight of the alkali-soluble resin (A21) is preferably 1.5 × 10 ³ to 40 × 10 ³ and more preferably 2.0 × 10 ³ to 20 × 10 ³ . When the mass average molecular weight is less than 1.5 × 10 ³ , curing during exposure may be insufficient, and when it exceeds 40 × 10 ³ , developability may be deteriorated.

The content of the alkali-soluble resin (A21) in the resin composition (NA) according to the present invention is preferably 10 to 90% by mass, more preferably 30 to 80% by mass with respect to the total solid content of the composition. Within this range, the developability of the photosensitive resin composition of the present invention is good.

(Crosslinkable resin (A22))
The crosslinkable resin (A22) is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group. By having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group, it can be crosslinked with the alkali-soluble resin (A21) to form a cured product. Moreover, when the following ink repellent agent has a carboxyl group and / or a hydroxyl group, it can also be cross-linked with the ink repellent agent to form a cured product.

The crosslinkable resin (A22) is preferably at least one selected from the group consisting of amino resins, epoxy compounds, and oxazoline compounds. These may be used alone or in combination of two or more.

Amino resins include compounds in which some or all of the amino groups such as melamine compounds, guanamine compounds, and urea compounds are hydroxymethylated, or some or all of the hydroxyl groups of the hydroxymethylated compounds are methanol, ethanol , A compound etherified with n-butyl alcohol, 2-methyl-1-propanol and the like, for example, hexamethoxymethylmelamine and the like.

Epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, brominated epoxy resin and other glycidyl ethers, 3,4- Alicyclic epoxy resins such as epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether, glycidyl esters such as diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl phthalate , Heterocyclic epoxies such as glycidylamines such as tetraglycidyldiaminodiphenylmethane and triglycidylparaaminophenol, and triglycidyl isocyanurate Shi resins.

Examples of the oxazoline compound include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl Mention may be made of copolymers of polymerizable monomers such as -4-methyl-2-oxazoline.

The content of the crosslinkable resin (A22) in the resin composition (NA) according to the present invention is preferably 1 to 50% by mass and more preferably 5 to 30% by mass with respect to the total solid content of the composition. Within this range, the developability of the photosensitive resin composition will be good.

(2-2) Photoactive agent (B): Photoacid generator (B2)
When the photosensitive resin composition of the present invention is a resin composition (NA), a photoacid generator (B2) that is a compound that generates an acid by light is used as the photoactivator (B). Examples of the photoacid generator (B2) include diaryliodonium salts, triarylsulfonium salts, triazine compounds, sulfonyl compounds, sulfonic acid esters, and the like.

Specific examples of the cation moiety of the diaryliodonium salt include diphenyliodonium, 4-methoxyphenylphenyliodonium, bis (4-t-butylphenyl) iodonium, and the like. Specific examples of the anion moiety of the diaryliodonium salt include trifluoromethanesulfonate, nonafluorobutanesulfonate, p-toluenesulfonate, pentafluorobenzenesulfonate, hexafluorophosphate, tetrafluoroborate, hexafluoroantimonate and the like. The diaryliodonium salt consists of a combination of one of the cation moieties and one of the anion moieties. For example, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate.

Specific examples of the cation moiety of the triarylsulfonium salt include triphenylsulfonium, diphenyl-4-methylphenylsulfonium, diphenyl-2,4,6-trimethylphenylsulfonium, and the like. Specific examples of the anion moiety of the triarylsulfonium salt include specific examples of the anion moiety of the diaryl iodonium salt. A triarylsulfonium salt consists of a combination of one of the cation moieties and one of the anion moieties. For example, triphenylsulfonium trifluoromethanesulfonate.

Specific examples of triazine compounds include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (2-furyl) ethenyl- bis (trichloromethyl) -1,3,5-triazine, 2- (5-methyl-2-furyl) ethenyl-bis (trichloromethyl)- Examples include 1,3,5-triazine and 2- (3,4-dimethoxyphenyl) ethenyl-bis (trichloromethyl) -1,3,5-triazine.

Specific examples of the sulfonyl compound include bis (phenylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and the like.

Specific examples of sulfonic acid esters include 2-nitrobenzyl p-toluenesulfonate, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, and the like.

The content of the photoacid generator (B2) in the resin composition (NA) according to the present invention is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the total solid content of the composition. preferable. Within this range, the developability of the photosensitive resin composition will be good. The proportion of the photoacid generator is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, based on the alkali-soluble binder resin. Within such a range, the curability and developability of the photosensitive composition will be good.

(2-3) Optional Component The resin composition (NA) according to the present invention comprises an alkali-soluble resin (A21) and a crosslinkable resin (A22) as the binder resin (A), and light as a photoactive agent (B). It contains the acid generator (B2), the fine particles (C), and the organic solvent (D), but may contain various optional components for the purpose of improving various functions within the range not impairing the effects of the present invention. Is possible.

As such optional components, all components other than the radical crosslinking agent among the optional components described in the resin composition (NR) can also be used in the resin composition (NA). Of these optional components, the optional components other than the ink repellent agent can be the same as the resin composition (NR) in terms of the type, blending amount, and preferred modes thereof.

As in the case of the resin composition (NR), examples of the ink repellent agent in the case of the resin composition (NA) include a fluorine-containing compound, a silicon-containing compound, and a compound having both a fluorine atom and a silicon atom. . Similarly to the above, a polymer having a fluoroalkyl group in the side chain is preferably used as the ink repellent, but in the case of the resin composition (NA), more preferably, in addition to the fluoroalkyl group, a carboxyl group and / or Alternatively, a polymer having a phenolic hydroxyl group in the side chain is used. The reason is that, similarly to the above, in the post-baking step of barrier rib formation by photolithography described later, the ink repellent agent reacts with other compounding components in the photosensitive composition and is fixed to the upper surface of the barrier rib. There is. In addition, the ink repellent agent is less likely to remain in the regions (dots) partitioned by the partition walls on the substrate when it has the above-mentioned acidic group, and the ink when the ink is injected by inkjet This is because the wet-spreading property of is good.

As a preferable embodiment of the ink repellent agent in the resin composition (NA), more specifically, at least one of the hydrogen atoms, preferably all of them are linear or branched having 20 or less carbon atoms substituted with fluorine atoms. Ink repellent agents comprising a polymer-like fluoroalkyl group (wherein the alkyl group includes those having etheric oxygen) and preferably a polymer having a carboxyl group and / or a phenolic hydroxyl group in the side chain. The acid value of the polymer having a carboxyl group and / or a phenolic hydroxyl group in the side chain in addition to the fluoroalkyl group is 5 from the viewpoints of immobilization on the partition wall and alkali solubility (removability from dots). -200 mgKOH / g is preferable, and 10-150 mgKOH / g is more preferable.

Furthermore, the polymer can have a silicone chain (straight chain) having about 200 or less silicon in the side chain. The preferred ranges of the fluorine content and the silicon content of the polymer used as the ink repellent agent in the resin composition (NA) are the same as the preferred ranges described for the polymer of the ink repellent agent in the resin composition (NR).

These ink repellents can be produced by a conventionally known method. Specifically, for a polymer having a fluoroalkyl group and a carboxyl group and / or a phenolic hydroxyl group in the side chain, JP-A-2005-315984 and the like describe the polymer having the fluoroalkyl group and the polymer having a silicone chain. Ink repellents combined with these can be produced by the method described in JP-A-2005-300759.

The content ratio of the ink repellent agent in the solid content of the resin composition (NA) containing the ink repellent agent is 0.01 with respect to the total solid content of the composition, as in the case of the resin composition (NR). It is preferably in the range of ˜30% by mass. The reason is that the obtained partition walls have good ink repellency, good wet spread in the dots of ink injected by the ink jet method, and good uniformity of the injected ink layer.

Further, the relationship between the ink repellent agent and the surfactant is the same as that of the resin composition (NR). Accordingly, it is preferable to add a surfactant to the resin composition (NA) for forming the partition for an optical element that performs pixel formation by a method other than the ink jet method. The surfactant similar to the case of a composition (NR) is mentioned. The blending amount can be the same as in the case of the resin composition (NR).

In the resin composition (NA) according to the present invention, the composition ratio of the total solid is alkali-soluble resin (A2): crosslinkable resin (A22): photoacid generator (B2): fine particles (C) = 10. -90% by mass: 1-50% by mass: 0.1-30% by mass: 3-35% by mass is preferable.
In the resin composition (NA) according to the present invention, the more preferable constitutional ratio of the total solid content is alkali-soluble resin (A2): crosslinkable resin (A22): photoacid generator (B2): fine particles (C). : Colorant (E): Optional component other than colorant (E) = 10 to 80% by mass: 1 to 50% by mass: 0.1 to 30% by mass: 3 to 35% by mass: 10 to 50% by mass: 1 21 to 50% by mass.

The resin composition (NA) according to the present invention is prepared by uniformly mixing the above-described various essential components and optional components added as necessary according to the above-mentioned blending amount by a normal method. be able to.

(3) Positive photosensitive resin composition containing o-quinonediazide compound When the photosensitive resin composition of the present invention is a positive photosensitive resin composition containing an o-quinonediazide compound, the photosensitive resin composition contains a binder resin. An alkali-soluble resin (A3) as (A), an o-quinonediazide compound (B3) as a photoactive agent (B), fine particles (C) in an organic solvent dispersion, and the fine particles (C) in the dispersion It contains fine particles (C) having a zeta potential of −100 to −5 mV as measured by an electrophoretic light scattering method, and an organic solvent (D) as essential components. Hereinafter, a positive photosensitive resin composition containing an o-quinonediazide compound is referred to as a resin composition (PQ).

The photosensitive composition from which the organic solvent (D) has been removed from the resin composition (PQ) increases the solubility of the o-quinonediazide compound in an aqueous alkali solution by actinic rays at the light-irradiated portion during exposure in photolithography, etc. In the subsequent development, it is dissolved and removed in the developer used, usually an alkali developer. A portion that is not irradiated with light (an unexposed portion) serves as a partition wall.

In addition, about the said microparticles | fine-particles (C) and organic solvent (D) which are the essential components which the resin composition (PQ) which concerns on this invention contains, said (1) resin composition (NR) about all types, compounding quantity, etc. ). Hereinafter, the essential components other than the fine particles (C) and the organic solvent (D) and the optional components will be described in this order.

(3-1) Binder resin (A): Alkali-soluble resin As the binder resin (A), a conventionally known binder resin (A): alkali-soluble resin is used for forming partition walls of the optical element in the resin composition (PQ). It is possible.

Examples of such alkali-soluble resins include phenol / formaldehyde resins, cresol / formaldehyde resins, phenol / cresol / formaldehyde co-condensation resins, phenol-modified xylene resins, polyhydroxystyrene, polyhalogenated hydroxystyrene, N- (4- Hydroxyphenyl) methacrylamide copolymers and hydroquinone monomethacrylate copolymers. In addition, various alkali-soluble polymer compounds such as sulfonylimide polymers, carboxyl group-containing polymers, acrylic resins containing phenolic hydroxyl groups, acrylic resins having sulfonamide groups, urethane resins, and the like may be used. it can.

Commercially available products can be used as the alkali-soluble resin. Examples of such commercially available products include EP4020G (trade name, manufactured by Asahi Organic Materials Co., Ltd.), CRG-951 (trade name, manufactured by Showa Kogyo Co., Ltd.), and polyhydroxystyrene as cresol novolac resins. It is done.

These alkali-soluble resins preferably have a mass average molecular weight of 500 to 60,000 and a number average molecular weight of 200 to 40,000. Moreover, you may use alkali-soluble resin in combination of 1 type or 2 types or more. Further, the content of the alkali-soluble resin as the binder resin (A) in the resin composition (PQ) is preferably 30 to 85% by mass, and 50 to 80% by mass with respect to the total solid content of the composition. More preferred.

(3-2) Photoactivator (B): o-quinonediazide compound The o-quinonediazide compound is a compound having at least one o-quinonediazide group and is particularly limited as long as it increases the solubility in an alkaline aqueous solution by actinic rays. Not. Specific examples of such an o-quinonediazide compound include a hydroxyl compound and o-benzoquinonediazide or a sulfonic acid ester of o-naphthoquinonediazide.

Examples of the o-quinonediazide compound described above include esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and phenol-formaldehyde resin or cresol-formaldehyde resin, 1,2-naphthoquinone-2-diazide. Esters of -5-sulfonyl chloride and pyrogallol / acetone resin, esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and resorcin-benzaldehyde resin, 1,2-naphthoquinone-2-diazide-5-sulfonyl Ester of chloride and resorcin-pyrogallol / acetone co-condensation resin, polyester having 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride esterified to a polyester having a hydroxyl group at its terminal, N- (4 1,2-naphthoquinone-2 esterified with 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride to a copolymer of hydroxyphenyl) methacrylamide homopolymer or other copolymerizable monomer -1,2-naphthoquinone-2-diazido-5-sulfonyl as a copolymer of diazide-5-sulfonyl chloride with bisphenol-formaldehyde resin, p-hydroxystyrene homopolymer or other copolymerizable monomer Examples of the esterified chloride include esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and polyhydroxybenzophenone.

The content of the o-quinonediazide compound (B3) as the photoactive agent (B) in the resin composition (PQ) is preferably 5 to 60% by mass with respect to the total solid content of the composition. The mass% is more preferable.

(3-3) Optional Component The resin composition (PQ) according to the present invention comprises an alkali-soluble resin (A3) as the binder resin (A), an o-quinonediazide compound (B3) as the photoactive agent (B), Although containing the fine particles (C) and the organic solvent (D), various optional components can be contained for the purpose of improving various functions and the like within a range not impairing the effects of the present invention.

As such optional components, all components other than the radical crosslinking agent among the optional components described in the resin composition (NR) can also be used in the resin composition (PQ). Of these optional components, the optional components other than the ink repellent agent can be the same as the resin composition (NR) in terms of the type, blending amount, and preferred modes thereof.

In the case of the resin composition (PQ), a preferred embodiment of the ink repellent includes a polymer having a fluoroalkyl structure and an acidic group. The reason for this is that the ink-repellent agent is less likely to remain in the dots and has better wettability when the ink is injected by the ink jet method when it has alkali solubility. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group. In such a polymer that becomes an ink repellent agent, the fluoroalkyl structure and the acidic group may be contained in the main chain of the polymer, in the side chain, and further in the main chain and the side chain. It may be included in both.

The content ratio of the ink repellent agent in the solid content of the resin composition (PQ) containing the ink repellent agent is preferably in the range of 0.01 to 30% by mass with respect to the total solid content of the composition. The reason is that the obtained partition walls have good ink repellency, good wet spread in the dots of ink injected by the ink jet method, and good uniformity of the injected ink layer.

Further, the relationship between the ink repellent agent and the surfactant is the same as that of the resin composition (NR). Accordingly, it is preferable to add a surfactant to the resin composition (PQ) for forming the partition for an optical element in which pixels are formed by a method other than the ink jet method. The surfactant similar to the case of a composition (NR) is mentioned. The blending amount can be the same as in the case of the resin composition (NR).

In the resin composition (PQ) according to the present invention, the constituent ratio of the total solid is alkali-soluble resin (A3): photoacid generator (B3): fine particles (C) = 30 to 85% by mass: 5 to 60% by mass: preferably 3 to 35% by mass.
Further, the more preferable composition ratio of the total solid content is as follows: alkali-soluble resin (A3): photoacid generator (B3): fine particles (C): colorant (E): optional components other than colorant (E) = 30 -80 mass%: 5-60 mass%: 3-35 mass%: 10-50 mass%: 1.21-50 mass%.

The resin composition (PQ) according to the present invention is prepared by uniformly mixing the above-described various essential components and optional components added as necessary according to the above-mentioned blending amount by a normal method. be able to.

(4) Positive photosensitive resin composition containing blocked acidic groups In the case where the photosensitive resin composition of the present invention is a positive photosensitive resin composition containing blocked acidic groups, the photosensitive resin composition Is a binder resin having a blocked acidic group as the binder resin (A), a photoacid generator as the photoactivator (B), and fine particles (C) in the organic solvent dispersion, Fine particles (C) having a zeta potential of −100 to −5 mV as measured by the electrophoretic light scattering method of the fine particles (C), and an organic solvent (D) are contained as essential components. Hereinafter, a positive photosensitive resin composition containing a blocked acidic group is referred to as a resin composition (PB).

In the photosensitive composition from which the organic solvent (D) is removed from the resin composition (PB), an acid is generated from the photoacid generator in the light irradiation portion during exposure in photolithography and the like, and is blocked by the action of the acid. The thus-formed binder resin having an acidic group becomes alkali-soluble, and is dissolved and removed in a developer to be used, usually an alkali developer, in the subsequent development. A portion that is not irradiated with light (an unexposed portion) serves as a partition wall.

Here, about the said microparticles | fine-particles (C) and the organic solvent (D) which are the essential components which the resin composition (PB) based on this invention contains, said (1) resin composition ( NR). Moreover, it can be made completely the same as that of the photoacid generator of said (2) resin composition (NA) about all the kind, compounding quantity, etc. of a photoacid generator.

(4-1) Binder Resin (A): Binder Resin Having Blocked Acid Group As a binder resin having a blocked acid group, a conventionally known resin in which an acid group of an alkali-soluble resin is blocked Is mentioned.

Examples of the acidic group in the blocked acidic group include a carboxylic acid group, a sulfonic acid group, a hydroxyl group bonded to a carbon atom to which two perfluoroalkyl groups and alkyl groups are bonded, and a hydroxyl group bonded to an aryl group. Preferred acidic groups are a carboxylic acid group, a hydroxyl group bonded to a carbon atom to which two trifluoromethyl groups are bonded, a hydroxyl group bonded to a carbon atom to which a trifluoromethyl group and a methyl group are bonded, and a hydroxyl group bonded to a phenyl group. . In the above, the aryl group or phenyl group may have a substituent, and the substituent is preferably a halogen atom, particularly a fluorine atom. The aryl group to which a hydroxyl group is bonded is preferably a polyfluorohydroxyphenyl group.

As the blocked part of the blocked acidic group, an alcoholic hydroxyl group of alcohols or phenols or a hydrogen atom of a phenolic hydroxyl group or a hydroxyl group of a carboxyl group, an alkyl group, an alkoxycarbonyl group, a trialkylsilyl group, an acyl group, Examples include a structure substituted with a cyclic ether group or the like. Preferable alkyl groups for substituting a hydrogen atom of a hydroxyl group include alkyl groups having 1 to 6 carbon atoms which may have a substituent (aryl group, alkoxy group, etc.).

Specific examples of these alkyl groups include alkyl groups having 6 or less carbon atoms (such as tert-butyl group), aryl group-substituted alkyl groups having 7 to 20 carbon atoms (benzyl group, triphenylmethyl group, p-methoxybenzyl group). Group, 3,4-dimethoxybenzyl group, 1-phenoxyethyl group, etc.), alkoxyalkyl groups having 8 or less carbon atoms (methoxymethyl group, 1-ethoxyethyl (2-methoxyethoxy) methyl group, benzyloxymethyl group, etc.) ). Preferable alkoxycarbonyl group for substituting a hydrogen atom of a hydroxyl group includes an alkoxycarbonyl group having a total of 8 or less carbon atoms, such as a tert-butoxycarbonyl group. A preferable trialkylsilyl group for substituting a hydrogen atom of a hydroxyl group is a trialkylsilyl group having a total carbon number of 10 or less, and includes a trimethylsilyl group. Preferred acyl groups for substituting the hydrogen atom of the hydroxyl group include acyl groups having a total carbon number of 8 or less, and examples thereof include a pivaloyl group, a benzoyl group, and an acetyl group. Preferred examples of the cyclic ether group for substituting the hydrogen atom of the hydroxyl group include a tetrahydropyranyl group.

Examples of the method for blocking acidic groups include a method of reacting alcohols, carboxylic acids, or active derivatives thereof according to the kind of acidic groups. Examples of these active derivatives include alkyl halides, acid chlorides, acid anhydrides, chlorocarbonates, 3,4-dihydro-2H-pyran and the like.

These binder resins having blocked acidic groups preferably have a mass average molecular weight of 500 to 60,000 and a number average molecular weight of 200 to 40,000. Further, the binder resin may be used alone or in combination of two or more. The content of the binder resin in the resin composition (PB) is preferably 30 to 90% by mass, and more preferably 50 to 85% by mass with respect to the total solid content of the composition.

(4-2) Optional Component The resin composition (PB) according to the present invention includes a binder resin having a blocked acidic group as the binder resin (A), and a photoacid generator as the photoactive agent (B). The fine particles (C) and the organic solvent (D) are contained, but various optional components can be contained for the purpose of improving various functions within a range not impairing the effects of the present invention.

As such optional components, all components other than the radical crosslinking agent among the optional components described in the resin composition (NR) can also be used in the resin composition (PB). Of these optional components, the optional components other than the ink repellent agent can be the same as the resin composition (NR) in terms of the type, blending amount, and preferred modes thereof.

In the case of the resin composition (PB), a preferable embodiment of the ink repellent agent is a polymer having a fluoroalkyl structure and having an acidic group at least after exposure. As such an ink repellent, specifically, a polymer having an acidic group blocked with a fluoroalkyl structure, or an alkali development resistance having a fluoroalkyl structure and an acidic group (easily from an unexposed portion during development). And a polymer having a molecular weight and an acid value adjusted so as to retain the same. For example, the reason is that when an acidic group is generated by exposure, the ink repellent agent hardly remains in the dot, and the ink spreads well when the ink is injected by an ink jet method. In addition, examples of the blocked acidic group include the same groups as described above.

Examples of the polymer having an acidic group blocked with a fluoroalkyl structure include, for example, fluoroalkyl groups disclosed in International Publication No. 2004/042474, International Publication No. 2007/069703, International Publication No. 2008/149976, and the like. And a copolymer of 2-tetrahydropyranyl methacrylate and the like. Further, the polymer can have a silicone chain (straight chain) having about 200 or less silicon in the side chain.

The content ratio of the ink repellent agent in the solid content of the resin composition (PB) containing the ink repellent agent is preferably in the range of 0.01 to 30% by mass with respect to the total amount of the solid content of the composition. The reason is that the obtained partition walls have good ink repellency, good wet spread in the dots of ink injected by the ink jet method, and good uniformity of the injected ink layer.

Further, the relationship between the ink repellent agent and the surfactant is the same as that of the resin composition (NR). Accordingly, it is preferable to add a surfactant to the resin composition (PB) for forming the partition for an optical element in which pixels are formed by a method other than the ink jet method. The surfactant similar to the case of a composition (NR) is mentioned. The blending amount can be the same as in the case of the resin composition (NR).

In the resin composition (PB) according to the present invention, the constituent ratio of the total solid content is such that the binder resin (A4) having a blocked acidic group: photoacid generator (B4): fine particles (C) = 30. -90% by mass: 0.1-30% by mass: 3 to 35% by mass is preferable.
Further, the more preferable composition ratio of the total solid content is as follows: alkali-soluble resin (A3): photoacid generator (B3): fine particles (C): colorant (E): optional components other than colorant (E) = 30 -90% by mass: 0.1-30% by mass: 3-35% by mass: 10-50% by mass: 1.21-50% by mass.

The resin composition (PB) according to the present invention is prepared by uniformly mixing the above-described various essential components and optional components added as necessary according to the above-mentioned blending amount by a normal method. be able to.

[Partition wall]
The partition of the present invention is a partition formed in the form of partitioning the substrate into a plurality of sections for pixel formation by photolithography using the photosensitive resin composition of the present invention, and is a color filter or organic EL It can be applied to a partition of an element, preferably a black matrix.

(substrate)
The substrate used for forming the partition wall of the present invention is not particularly limited, but is usually a material used for a substrate for an optical element, for example, various glass plates; polyester (polyethylene terephthalate, etc.), Thermoplastic plastic sheets such as polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, poly (meth) acrylic resin; thermosetting plastic sheets such as epoxy resin and unsaturated polyester . Moreover, the board | substrate which formed insulating films, such as a silicon nitride and a polyimide, in the said base material previously can be mentioned. In particular, a heat resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance.

In the present invention, the photosensitive resin composition of the present invention was used when the substrate having a surface property that had good affinity with the alkali developer used in the photolithography method as the partition wall was used as the substrate. The effect of pattern development adhesion can be made more remarkable.
Here, good affinity with an alkali developer means a case where the contact angle of water is 70 ° or less. Further, when the contact angle of water is 50 ° or less, particularly when the contact angle of water is 30 ° or less, the effect of developing adhesion of the pattern using the photosensitive resin composition of the present invention becomes more remarkable. be able to. Further, as the type of the substrate, when the substrate surface has a hydrophilic functional group such as a hydroxyl group and is a glass substrate such as a glass substrate such as alkali-free glass or alkali glass, the photosensitivity of the present invention. The effect of developing adhesion of the pattern using the resin composition can be made more remarkable.

Further, the part where the partition wall of the present invention is formed is not particularly limited as long as it is on the substrate. That is, in this specification, “formed on the substrate” means that, for example, when a wiring or other functional layer is formed on the substrate, it is formed on the wiring or functional layer further on the substrate. Means that.

Hereinafter, as an example of a method for producing a partition wall of the present invention, a method for producing a partition wall by a photolithography process using the photosensitive resin composition of the present invention will be described. (1) Partition formation of a negative photosensitive resin composition 1 (a1) to (c1) schematically showing the method, and (2) FIGS. 1 (a2) to (c2) schematically showing the method of forming the partition walls of the positive photosensitive resin composition. To do.

(Formation of wet film made of photosensitive resin composition on substrate = application step)
First, in order to form a wet film of the photosensitive resin composition on the substrate, the photosensitive resin composition is applied to a predetermined position on the substrate (hereinafter referred to as “application process”). Examples of the coating method include conventionally known methods such as spin coating, spraying, slit coating, roll coating, spin coating, and bar coating.

Here, the film thickness of the wet film of the photosensitive resin composition obtained in the coating step depends on the type of the photosensitive resin used, the solid content concentration, the partition wall forming method described below, etc., but is finally obtained. The thickness is set such that the height of the partition wall becomes a desired value, for example, about 2 to 20 times the desired value.

That is, in the optical element obtained by the production method of the present invention, the height of the partition wall finally obtained is preferably 0.05 to 50 μm, although it depends on the type of the optical element. From 10 to 10 μm is more preferable, and from 0.5 to 5 μm is most preferable. Therefore, the photosensitive resin composition is applied so that the height of the partition wall finally obtained is the above-described height.

(Drying / Prebaking process)
Next, the wet film | membrane of the photosensitive resin composition formed on the board | substrate is dried. By drying the wet film, the organic solvent (D) is volatilized and a layer of a photosensitive composition with little tackiness is formed. When the photosensitive resin composition contains a low boiling point compound other than the organic solvent (D), it is removed together with the organic solvent (D).

In the case where the organic solvent (D) contained in the photosensitive resin composition is volatilized and removed, vacuum drying or heat drying is preferably performed. Further, in order to efficiently dry the photosensitive composition layer without causing uneven appearance, it is more preferable to use vacuum drying and heat drying in combination. Although it varies depending on the type of each component, the blending ratio, etc., vacuum drying is preferably performed at about 500 to 10 Pa for about 10 to 300 seconds, and heat drying at about 50 to 120 ° C. for about 10 to 2,000 seconds.

FIGS. 1A1 and 1A2 show a state after a negative photosensitive resin composition and a positive photosensitive resin composition are applied to a substrate and dried (the wet film is a layer of the photosensitive composition). It is sectional drawing of the board | substrate 1 and the layer 2 of the photosensitive composition which show the state which became.

(Exposure process)
Next, a part of the layer of the photosensitive composition is exposed. The exposure is preferably performed through a mask having a predetermined pattern. As the irradiation light, visible light; ultraviolet light; far ultraviolet light; excimer laser such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser, Kr ₂ excimer laser, KrAr excimer laser, Ar ₂ excimer laser; X-ray; Etc. An electromagnetic wave having a wavelength of 100 to 600 nm is preferable, a light ray having a distribution in the range of 300 to 500 nm is more preferable, and i-line (365 nm), h-line (405 nm), and g-line (436 nm) are particularly preferable.

FIG. 1 (b1) shows that the negative photosensitive composition layer 2 after being dried as necessary on the substrate 1 is irradiated with light 4 through a mask 3 having a predetermined pattern, and the mask 3 is cut. FIG. 4 is a cross-sectional view showing an exposure process in which light 4 is transmitted through only a predetermined pattern portion and reaches a layer 2 of a negative photosensitive composition on a substrate 1 and only an exposed portion 5 is photocured. The unexposed portion 6 not irradiated with light is in the state of the negative photosensitive composition and exhibits alkali solubility.
In addition, FIG.1 (b2) is sectional drawing which shows the exposure process at the time of using a positive photosensitive resin composition. In this case, the exposed portion 5 where the light reaches the layer 2 of the positive photosensitive composition becomes alkali-soluble by the photoreaction. The unexposed portion 6 that has not been irradiated with light is in the state of the positive photosensitive composition and exhibits alkali development resistance.

As the irradiation device, a known ultra-high pressure mercury lamp, deep UV lamp, or the like can be used. Exposure is preferably in the range of 5 ~ 1,000mJ / cm ^2, more preferably 10 ~ 200mJ / cm ^2. When the exposure amount is too low, in the case of a negative photosensitive composition, the exposed portion 5 is not sufficiently cured, and there is a possibility that dissolution or peeling will occur in subsequent development. On the other hand, in the case of a positive photosensitive composition, the alkali solubility in the exposed part becomes insufficient, and a development residue may be generated. When the exposure amount is too high, high resolution tends not to be obtained even in the case of a negative photosensitive composition or a positive photosensitive composition.

In the case where a resin composition (NA) or a positive photosensitive resin composition is used after exposure and before development, it is preferable to heat-treat the photosensitive composition layer in order to accelerate the reaction. The heating temperature is 50 to 140 ° C. and 10 to 2,000 seconds. This is a process generally called PEB (Post Exposure Bake). This PEB is a heat treatment performed as a treatment for diffusing an acid generated by exposure in a layer of a photosensitive composition formed from a resin composition (NA) or a positive photosensitive resin composition.

(Development process)
When the negative photosensitive resin composition is used after developing with a developer after the exposure step, the unexposed portion 6 of the photosensitive composition layer is removed and the positive photosensitive resin composition is used. In the step, the exposed portion 5 of the layer of the photosensitive composition is removed. As the developer, for example, an alkali aqueous solution containing an alkali metal hydroxide such as potassium hydroxide, an alkali metal carbonate such as potassium carbonate, an alkali such as an amine, an alcohol amine or a quaternary ammonium salt is used. Can do.

Develop time (time for contacting with developer) is preferably 5 to 180 seconds. Further, the developing method may be any of a liquid piling method, a dipping method, a shower method and the like. After development, water on the substrate can be removed by performing high-pressure water washing or running water washing and air-drying with compressed air or compressed nitrogen.

In this way, after the exposure step, development is performed using a developer, and when the negative photosensitive resin composition is used, the photosensitive composition on the substrate 1 shown in FIG. The unexposed portion 6 of the layer is removed, and the structure of the partition wall 8 composed of the substrate 1 and the exposed portion 5 on the substrate is obtained as shown in the sectional view of FIG. When a positive photosensitive resin composition is used, the exposed portion 5 of the layer of the photosensitive composition on the substrate 1 shown in FIG. 1 (b2) is removed, and the substrate 1 and the substrate are not yet exposed. The structure of the partition 8 which consists of the exposure part 6 is obtained. Note that a portion surrounded by the partition wall 8 and the substrate 1 is a portion indicating the dot 7 in which an ink layer, that is, a pixel is formed by ink injection or the like.

In the partition wall of the present invention, when the unexposed portion 6 of the photosensitive composition layer is removed with a developer by using the negative photosensitive resin composition of the present invention, the photosensitive composition layer is used. Since the exposed portion 5 (partition wall 8) of FIG. 5 is sufficiently in contact with the substrate 1, the developer does not enter the interface between the two, so that the partition wall 8 may partially peel from the substrate 1. As a result, a high-resolution pattern can be formed. When the positive photosensitive resin composition of the present invention is used, when the exposed portion 5 of the photosensitive composition layer is removed with a developer, the unexposed portion 6 of the photosensitive composition layer is removed. Since the (partition wall 8) is in a sufficiently close contact with the substrate 1, the developer does not enter the interface between the two, so that the partition wall 8 does not partially peel from the substrate 1, and as a result High-resolution pattern formation is possible.

When the negative photosensitive resin composition used for the partition formation contains an ink repellent agent, a layer (not shown) in which the ink repellent agent is unevenly distributed on the upper surface layer of the partition wall 8 shown in FIG. ) Is formed. When the positive photosensitive resin composition used for forming the partition contains an ink repellent, a layer (not shown) in which the ink repellent is unevenly distributed on the upper surface layer of the partition 8 shown in FIG. 1 (c2). It is formed. The layer in which the ink repellent agent is unevenly distributed is an organic solvent from the wet film in the drying step because the ink repellent agent that was uniformly dissolved in the photosensitive resin composition at the beginning of the partition wall forming step has characteristics of the ink repellent agent. It is formed by moving to the upper part of the layer of the photosensitive composition along with the volatilization removal of (D) and being fixed to the upper surface of the layer by exposure.

(Post-baking process)
Subsequently, it is preferable to heat the partition wall 8 on the substrate 1. Examples of the heating method include a method in which the partition wall 8 is heat-treated at 150 to 250 ° C. for 5 to 90 minutes with a heating device such as a hot plate or an oven together with the base material 1. By this heat treatment, the partition walls 8 on the substrate 1 are sufficiently cured, and the shape of the dots 7 surrounded by the partition walls 8 and the substrate 1 is further fixed. In addition, it is more preferable that the temperature of this heat processing is 180 degreeC or more. If the heating temperature is too low, curing of the partition walls 8 is insufficient, so that sufficient chemical resistance cannot be obtained. Thereafter, for example, when ink is injected into the dots 7 in the inkjet coating process, it is included in the ink. The solvent may cause the partition wall 8 to swell or the ink to ooze. On the other hand, if the heating temperature is too high, thermal decomposition of the partition wall 8 may occur.

In the partition wall of the present invention, the development adhesiveness of the partition wall is improved by using the photosensitive resin composition of the present invention. At the same time, by adjusting the blending amount of the fine particles (C) in the photosensitive resin composition, it is possible to impart shape stability against heat to the partition walls 8 in the post-baking step. As a result, if the development adhesion of the partition walls is improved and the generation of thermal flow is suppressed, a pattern with higher resolution can be formed as a result.

The photosensitive resin composition of the present invention can form a pattern with high resolution as described above, and can be used for pattern formation in which the average width of the partition walls is preferably 100 μm or less, more preferably 50 μm or less. In particular, a pattern of 15 μm or less can be formed. Moreover, the average of the distance (dot width) between adjacent partition walls (black matrix) is preferably 1,000 μm or less, more preferably 500 μm or less. The average height of the partition walls (black matrix) is preferably 0.05 to 50 μm, more preferably 0.2 to 10 μm.

Opening one volume, preferably a 500 ~ 3,000,000μm ^3, more preferably from 1,500 ~ 1,500,000μm ^3, particularly preferably at 3,000 ~ 500,000μm ³ is there. If the volume of the openings (dots) is too small, it is difficult to fill the desired dots with ink when used in the ink jet method. On the other hand, if the volume of the dots is too large, it is difficult to uniformly fill the filled ink with the dots.

Note that the size of the partition walls and pixels in the optical element varies depending on the type of the optical element. For example, the pixel area of a 42-inch television is approximately 75,000 μm ² , and the pixel area of a 32-inch television is approximately 30,000 μm ² . The film thickness of the color filter is approximately 1 to 3 μm, and the film thickness of the organic EL is approximately 0.1 to 1 μm. Considering these, the volume range of the opening is about 500 to 3,000,000 μm ³ described above.

Specific examples of the optical element to which the partition wall of the present invention is preferably applied include a color filter and an organic EL element. Hereinafter, application of the partition of the present invention in these optical elements will be described.

[Color filter]
The color filter of the present invention is a color filter having a plurality of pixels and a partition located between adjacent pixels on the substrate, wherein the partition is formed of the partition of the present invention. In the color filter of the present invention, the partition walls are preferably a black matrix having an optical density of about 2 to 7.

As described above, in the color filter of the present invention, after forming a partition, for example, a black matrix, on the substrate, an ink is applied to the opening of the partition by an ordinary method such as an inkjet method or a photolithography method. It can be manufactured by forming pixels.

The arrangement of the pixels is not particularly limited, and examples thereof include known arrangements such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type. The partition wall is formed in accordance with the shape of the pixel.

Here, when the color filter of the present invention is manufactured, after the partition is formed, before the ink is put into the partition on the substrate, for example, the region (dot) partitioned by the black matrix, The exposed base material surface may be subjected to an ink affinity treatment by a method such as cleaning with an alkaline aqueous solution, UV cleaning, UV ozone cleaning, excimer cleaning, corona discharge, or oxygen plasma.

(Pixel formation by inkjet method)
In order to form a pixel by an inkjet method in a region partitioned by a black matrix on a substrate, first, R (red) is applied to the dot after the ink-repellent treatment step is performed by the inkjet method as necessary. B (blue) and G (green) inks of three colors are injected. The ink can be injected in the same manner as a normal method using an ink jet apparatus generally used in the ink jet method. The ink jet device used for such ink injection is not particularly limited, but a method in which charged ink is continuously ejected and controlled by a magnetic field, and a method in which ink is intermittently ejected using a piezoelectric element. Ink jet apparatuses using various methods such as a method of heating ink and intermittently ejecting the ink by using the bubbling can be used.

In this specification, “ink” means a liquid material or a solid material (for example, a solution or dispersion liquid in the case of a solid material) having an optically and electrically function after being dried (or cured). It is a collective term and is not limited to coloring materials conventionally used. Similarly, “pixels” formed by injecting the ink are also used to represent sections having optical and electrical functions, which are partitioned by the partition walls.

Here, the ink used for forming the pixel of the color filter mainly includes a coloring component, a binder resin component, and a solvent. As the coloring component, it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like. As the binder resin component, a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin. The water-based ink contains water and, if necessary, a water-soluble organic solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary. The oil-based ink contains an organic solvent as a solvent, a resin soluble in an organic solvent as a binder resin component, and various auxiliary agents as necessary.

In the ink jet method, it is preferable to perform drying, heat curing, and ultraviolet curing, if necessary, after injecting ink into the dots by the ink jet apparatus.

(Pixel formation by photolithography)
In order to form a pixel by a photolithography method in a region partitioned by a black matrix on a base material, the substrate is first cleaned as necessary, and then a color ink composition is added as in the black matrix manufacturing method. Apply to substrate. The coating method is the same as the coating method in the black matrix manufacturing method. After that, a color layer is formed on the dots through the pre-baking process, the exposure process, the developing process, and the post-baking process as described above. This process is performed for each of the three ink colors R (red), B (blue), and G (green) (three times in total) to complete the pixel.

The ink mainly contains a coloring component, a binder resin component, and a solvent, and may be either water-based ink or oil-based ink. As the coloring component, pigments and / or dyes excellent in heat resistance, light resistance and the like are preferable. As the binder resin component, a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin. The water-based ink contains water as a solvent and, if necessary, a water-soluble organic solvent, and contains a water-soluble resin and / or a water-dispersible resin as a binder resin component. The oil-based ink contains an organic solvent as a solvent, and a resin soluble in the organic solvent as a binder resin component.

Thus, after forming pixels by partitioning on the base material, for example, a region partitioned by a black matrix, by an inkjet method, a photolithography method or the like, a protective film layer is formed as necessary. The protective film layer is preferably formed for the purpose of increasing the surface flatness and for blocking the eluate from the ink in the partition walls and the pixel portion from reaching the liquid crystal layer. When forming the protective film layer, it is preferable to remove the ink repellency of the partition wall in advance. Unless the ink repellency is removed, the coating liquid for overcoat is repelled and a uniform film thickness cannot be obtained, which is not preferable. Examples of the method for removing the ink repellency of the partition include plasma ashing and optical ashing.

Furthermore, in order to improve the quality of the liquid crystal panel manufactured using the color filter of the present invention, a photo spacer may be formed on a partition wall, for example, a black matrix, if necessary.

[Organic EL device]
The organic EL element of the present invention is an organic EL element having a plurality of pixels and a partition located between adjacent pixels on a substrate, wherein the partition is formed of the partition of the present invention. To do.

The organic EL device of the present invention can be manufactured as follows. First, using a sputtering method or the like, a transparent electrode such as ITO is formed on a transparent substrate such as a glass substrate, and the transparent electrode is etched into a desired pattern as necessary. Next, in the same manner as in the case of the color filter, a partition, for example, a black matrix is formed on the substrate, and then a hole transport material is used as an ink in the opening of the partition (black matrix) using an ink jet method. The solution of the above and the solution of the light emitting material are sequentially applied and dried to form a hole transport layer and a light emitting layer. Furthermore, an organic EL element is obtained by forming an electrode, such as aluminum, using a vapor deposition method or the like to form a pixel. Note that the formation of the pixels is not limited to the inkjet method, and may be performed by a photolithography method.

[Manufacture of organic EL lighting elements]
It can be produced in the same manner as in the production of the organic EL display element. The light emitting layer may be formed by laminating light emitting bodies that develop colors such as red, green, and blue by ink jetting, or the light emitting bodies may be separately coated on a plane.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “part” means mass part, and “%” means mass%.
The abbreviations of the compounds used in the following examples are shown below.

[1] Compound (monomer) used for production of ink repellent agent
_{_{C6FMA: CH 2 = C (CH}} 3) COOCH 2 CH 2 (CF 2) 6 F
MAA: methacrylic acid 2-HEMA: 2-hydroxyethyl methacrylate PME400: BLEMMER PME-400 (manufactured by NOF Corporation, CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) _k CH ₃ : k in the formula is (The average value between molecules is shown, and the value of k is about 9.)
GMA: Glycidyl methacrylate AOI: Karenz AOI (trade name, Showa Denko, 2-acryloyloxyethyl isocyanate)

(Polymerization initiator, catalyst, polymerization inhibitor)
V-65: V-65 (Wako Pure Chemical Industries, 2,2'-azobis (2,4-dimethylvaleronitrile))
DBTDL: Dibutyltin dilaurate TBQ: tert-butyl-p-benzoquinone (solvent)
MEK: 2-butanone

[2] Photosensitive resin composition component (binder resin (A))
(For resin composition (NR))
EX1010: EX-1010 (trade name, manufactured by Nagase ChemteX Corporation, resin solution in which an ethylenic double bond and an acidic group are introduced into the epoxy resin represented by the general formula (2), solid content: 60% by mass, (Mass average molecular weight: 3,020)
ZCR1569H: KAYARAD ZCR-1569H (trade name, manufactured by Nippon Kayaku Co., Ltd., a resin solution in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the general formula (1); solid content : 70% by mass, mass average molecular weight: 4,710)
ZCR1642H: ZCR-1642H (trade name, manufactured by Nippon Kayaku Co., Ltd., a solution of a resin in which an ethylenic double bond and an acidic group are introduced into an epoxy resin having a biphenyl skeleton represented by the general formula (1); solid content: 60 mass%, mass average molecular weight: 7,900)
ZAR2001H: ZAR-2001H (trade name, a solution of a resin in which an ethylenic double bond and an acidic group are introduced into a bisphenol A type epoxy resin; solid content: 65% by mass, mass average molecular weight: 10,000)
(Resin composition (NA) and positive photosensitive resin composition, alkali-soluble resin)
EP4020G: EP4020G (Asahi Organic Materials Industries Co., Ltd., cresol novolac resin; mass average molecular weight: 11,570)
(For resin composition (NA), crosslinkable resin)
NW100LM: Nikarac NW-100LM (Sanwa Chemical Co., Hexamethoxymethylol Melamine)

(Photoactive agent (B))
OXE02: OXE02 (trade name, manufactured by Ciba Specialty Chemicals, Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime) (general formula In (4), R ²¹ and R ²² are methyl groups, R ²³ is an ethyl group, R ²⁴ , R ²⁶ and R ²⁷ are hydrogen atoms, and R ²⁵ is a 2-methylbenzoyl group)
NCI831: Adeka Arcles NCI-831 (trade name, manufactured by ADEKA, oxime esters)
TFE triazine: TFE-triazine (2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine)
4NT-250: 4NT-250 (Toyo Gosei Co., Ltd., ester compound of 2,3,4,4′-tetrahydroxybenzophenone and 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid)

(Dispersion of fine particles (C))
NPCST: Organosilica sol (trade name, manufactured by Nissan Chemical Industries, zeta potential: -15 mV, average particle size: 24 nm, dispersion medium: ethylene glycol monopropyl ether, solid content: 30% by mass)
IPAST: Organosilica sol (trade name, manufactured by Nissan Chemical Industries, zeta potential: -28 mV, average particle size: 45 nm, dispersion medium: 2-propanol, solid content: 30% by mass)
PMAST: Organosilica sol (trade name, manufactured by Nissan Chemical Industries, zeta potential: -3 mV, average particle size: 26 nm, dispersion medium: PGMEA, solid content: 30% by mass)

<Measurement of zeta potential>
The zeta potential was measured by ELSZ series of a zeta potential measurement system manufactured by Otsuka Electronics Co., Ltd. after each dispersion was diluted 50,000 times with a dispersion medium of each fine particle. The zeta potential was calculated from the Huckle equation using the physical properties of the following solvents. The SP value of each dispersion medium is also shown.
Ethylene glycol monopropyl ether: refractive index 1.413, viscosity 2.04 (mPa · s), dielectric constant 10.92, SP value 11.1 (cal / cm ³ ) ^1/2
2-propanol: Refractive index 1.378, viscosity 1.96 (mPa · s), dielectric constant 18.30, SP value 11.6 (cal / cm ³ ) ^1/2
PGMEA: Refractive index 1.400, viscosity 1.10 (mPa · s), dielectric constant 8.30, SP value 8.7 (cal / cm ³ ) ^1/2

(Colorant (E))
CB: carbon black dispersion (average secondary particle size 120 nm, dispersion medium: PGMEA, carbon black: 20% by mass, polyurethane polymer dispersant having an amine value of 18 mgKOH / g: 5% by mass)
Mixed organic pigment: C.I. I. Pigment blue 15: 6, C.I. I. Pigment red 254, C.I. I. CI Pigment Yellow 139, 10: 5: 5: 5 mixture of polymer dispersant, solid content: 25% by mass, dispersion medium: PGMEA)
(Surfactant)
BYK306: BYK-306 (trade name, manufactured by BYK Japan, Inc., 12% by mass solution of polyether-modified polydimethylsiloxane (xylene / monophenyl glycol (7/2))
(Radical crosslinking agent)
A-BPEF: NK ester A-BPEF (Shin-Nakamura Chemical Co., Ltd., 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene)
UX5002D: KAYADAD UX-5002D (manufactured by Nippon Kayaku Co., Ltd., urethane acrylate)
(Thermal crosslinking agent)
NC3000H: NC-3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy resin having a biphenyl skeleton represented by general formula (1))
(Silane coupling agent)
KBM403: Trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane (phosphate compound)
PA: 2: 1 (mass ratio) mixture of phosphoric acid and monomethacryloyloxyethyl phosphate, dimethacryloyloxyethyl phosphate (solvent)
PGMEA: Propylene glycol 1-monomethyl ether 2-acetate

<Synthesis of ink repellent>
[Synthesis of ink repellent agent (E-1)]
To an autoclave with an internal volume of 1 L equipped with a stirrer, MEK (420.0 g), C6FMA (99.0 g), MAA (9.0 g), PME400 (63.0 g), GMA (9.0 g), and polymerization start Agent V-65 (0.3 g) was charged and polymerized at 50 ° C. for 24 hours with stirring under a nitrogen atmosphere to synthesize a crude copolymer. Hexane was added to the obtained crude copolymer solution for purification by reprecipitation, followed by vacuum drying to obtain an ink repellent agent (E-1) (162.3 g).
The ink repellent agent (E-1) had a number average molecular weight of 64,700, a mass average molecular weight of 94,020, a fluorine atom content of 31.4% by mass, and an acid value of 32.6 mgKOH / g. .

[Synthesis of ink repellent agent (E-2)]
MEK (420.0 g), C6FMA (81.0 g), 2-HEMA (36.0 g), PME400 (54.0 g), MAA (9.0 g) and polymerization in an autoclave with an internal volume of 1 L equipped with a stirrer Initiator V-65 (1.1 g) was charged and polymerized at 50 ° C. for 24 hours with stirring in a nitrogen atmosphere to obtain a polymer solution. The obtained polymer had a number average molecular weight of 34,200 and a mass average molecular weight of 63,900.

The polymer solution (500.0 g), AOI (32.6 g), DBTDL (0.13 g), TBQ (1.6 g) and MEK (17.1 g) were placed in a 1 L autoclave equipped with a stirrer. The mixture was allowed to react at 40 ° C. for 24 hours while charging and stirring. Hexane was added to the reaction solution for reprecipitation purification, followed by vacuum drying to obtain an ink repellent agent (E-2) (165.0 g). The ink repellent agent (E-2) has a number average molecular weight of 34,900, a mass average molecular weight of 69,300, a fluorine atom content of 21.1% by mass, and an ethylenic double bond content of 1.26 ×. The acid value was 10 ⁻³ mol / g and the acid value was 26.8 mgKOH / g.

Various physical properties of the ink repellent obtained above were measured by the following methods.
<Molecular weight>
The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by gel permeation chromatography using polystyrene as a standard substance.
<Fluorine atom content>
The fluorine atom content in the polymer was calculated from the charged value of the polymerization reaction.
<Content of ethylenic double bond>
The content of ethylenic double bonds in the polymer was calculated by ¹ H NMR measurement using 1,4-ditrifluoromethylbenzene as a standard substance.
<Acid value>
The acid value is a theoretical value calculated from the blending ratio of monomers as raw materials.

[Example 1]
EX1010 (28.4% in solid content) as binder resin (A), OXE02 (6.1% in solid content) as photoactive agent (B), NPCST (solid content) as dispersion of fine particles (C) CB as a colorant (E) (32.5% in solid content, and the solid content also includes a polyurethane-based polymer dispersant), (E-2) as an ink repellent agent ( 0.6% solids), A-BPEF as radical crosslinking agent (8.1% solids), NC3000 as thermal crosslinking agent (4.1% solids), and solids concentration 15 mass PGMEA was mixed so that it might become%, and the resin composition (NR) was manufactured.

As a glass substrate, AN100 (manufactured by Asahi Glass Co., Ltd.) was irradiated with ultraviolet rays for 2 minutes using a low-pressure mercury lamp. The water contact angle of the substrate was measured and found to be 5 ° or less.
After applying the photosensitive resin composition onto the glass substrate using a spinner, the photosensitive resin composition was dried on a hot plate at 100 ° C. for 2 minutes to form a photosensitive composition layer having a thickness of 2.0 μm. Next, using an ultra-high pressure mercury lamp, the photosensitive composition layer was exposed to light having an exposure dose of 50 mJ / cm ^{2 on} the basis of i-line (365 nm) through a mask. The mask has a design in which light transmitting portions and light shielding portions are alternately arranged in a line. The light transmitting portions are 5 μm, 10 μm, and 15 μm, and the light shielding portions are 100 μm.

Next, development was performed using a developing machine. As the developer, a 0.4% TMAH (tetramethylammonium hydroxide) aqueous solution was used. Thereafter, the unexposed portion was washed away with water and dried. Next, the glass substrate sample (1) of Example 1 in which the partition walls were formed was obtained by heating (post-baking) the glass plate in an oven at 220 ° C. for 30 minutes.

A glass substrate sample of Example 1 in which a cured product of the photosensitive composition was formed in the same manner as described above except that the mask was changed to a lattice pattern having a light shielding part of 150 μm × 400 μm and a light transmission part of 20 μm. 2) was obtained. The volume of the formed opening was 120 pL. Further, a glass substrate sample (3) of Example 1 on which a cured product of the photosensitive composition was formed was obtained in the same manner as above except that the exposure was performed without using a mask.

[Examples 2 to 4, 6]
The resin compositions (NR) of Example 2, Example 3, and Example 6 and the resin composition of Example 4 were the same as Example 1, except that the formulation of each component was changed as shown in Table 2. A product (NA) was produced.

A partition made of a cured product of the photosensitive composition in the same manner as in Example 1, except that the photolithography process and the film forming conditions were changed as shown in Table 2 using the obtained negative photosensitive resin composition. A glass substrate sample (1) of Examples 2 to 4 having formed thereon was obtained. PEB is a process of heating after exposure and before development.
In addition, glass substrate samples (2) and (3) were produced in the same manner as in Example 1 using the negative photosensitive resin compositions obtained in Example 3, Example 4, and Example 6.

[Example 5]
A resin composition (PQ) of Example 5 was produced in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 2. Further, using the obtained positive photosensitive resin composition, the mask is designed such that the light transmitting portions and the light shielding portions are alternately arranged in a line, and the light shielding portions are 5 μm, 10 μm, and 15 μm. Example in which partition walls made of a cured product of the photosensitive composition were formed in the same manner as in Example 1 except that a mask having a thickness of 100 μm was used and the photolithography process and the film forming conditions were changed as shown in Table 2. A glass substrate sample (1) of Example 5 was produced.

[Comparative Examples 1 and 2]
Resin compositions (NR) of Comparative Examples 1 and 2 were produced in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 2.
A partition made of a cured product of the photosensitive composition in the same manner as in Example 1, except that the photolithography process and the film forming conditions were changed as shown in Table 2 using the obtained negative photosensitive resin composition. Glass substrate samples (1), (2), and (3) of Comparative Examples 1 and 2 in which were formed.

[Evaluation method and evaluation results]
With the method described below, the resolution and thermal flow were evaluated using the glass substrate samples (1) produced in the above examples and comparative examples. Moreover, ink was injected by the inkjet method using the glass substrate sample (2) produced in Examples 1, 3, 4, 6 and Comparative Examples 1 and 2, and the ink layer uniformity was evaluated. Ink repellency was evaluated using the glass substrate samples (3) produced in Examples 1, 3, 4, and 6 and Comparative Examples 1 and 2. The evaluation results are shown in Table 2.

<Development adhesion>
In the glass substrate sample (1), a sample in which a 5 μm line remained was evaluated as “◯” (good), and a sample in which all the 5, 10, and 15 μm lines were peeled off and was not left as “×” (impossible). .

<Thermal flow>
Using the glass substrate sample (1) after development and before post-baking and after post-baking, the cross-sectional shapes of the lines were observed and compared with SEM. The case where the partition wall was thermally flown before and after the post-baking was evaluated as “×” (impossible), the case where the thermal flow was somewhat thermal was evaluated as “◯” (good), and the case where no thermal flow was performed was evaluated as “「 ”(excellent).

<Liquid repellency>
The liquid repellency was evaluated by measuring the contact angle of PGMEA on the surface of the cured product of the glass substrate sample (3).
The contact angle is an angle formed by a solid surface and a tangent to the liquid surface at a point where the solid and the liquid come into contact, and is defined as an angle on the side including the liquid. For this reason, it means that liquid repellency of hardened | cured material is excellent, so that a contact angle is large.

<Ink layer uniformity after inkjet>
Liquid epoxy ME-562 (Nippon Pernox) (6.25 g), curing agent HV-562 (Nippon Pernox) (6.25 g), diethyl adipate (12.5 g) and diethyl malonate (25.0 g) ) Was stirred and mixed using a stirrer for 1 hour to produce an ink.
Using the ink jet method, the ink produced above was applied to the opening between the partition walls of the glass substrate sample (2) in Examples 1, 4, 6 and Comparative Examples 1 and 2, about 120 pL, and in Example 3 about 180 pL. .

[Ink layer partition wall thickness (Mave)]
The film thickness at the partition wall of three pixels of each test optical element, ie, the ink layer, was measured using an ultradeep shape measuring microscope VK-8500 (manufactured by Keyence Corporation). As shown in FIGS. 2 (a) and 2 (b), the measurement points are four points on the central partition wall of each side, that is, the points y1 to y4 shown in FIG. 2 (b). The thickness at the ink layer partition wall (M) in the pixel was determined, and the average value of the three measured pixels was defined as the ink layer partition wall thickness (Mave).

[Ink layer center film thickness (Nave)]
The film thickness at the center of each of the three test optical elements, that is, the ink layers, was measured using an ultradeep shape measuring microscope VK-8500 (manufactured by Keyence Corporation). The measurement location is as shown in FIGS. 2A and 2B for each pixel, and the measured value is measured at the center of the ink layer in that pixel, the film thickness (N) at the position x shown in FIG. did. Further, the average value of the three pixels measured was defined as the ink layer partition wall thickness (Nave).

[Ink layer uniformity]
It calculated with the following formula from the value of Mave and Nave obtained above.
Mave / Nave × 100
A sample having Mave / Nave × 100 of 80 or more was evaluated as “◎” (excellent), a sample of 60 or more and less than 80 was evaluated as “◯” (good), and a sample of less than 60 was evaluated as “×” (impossible).

As can be seen from Table 2, in Examples 1 to 6 using NPCST or IPAST having a zeta potential of −5 mV or less as the fine particles (C), a 5 μm line remains after development and the resolving power is good. On the other hand, in Comparative Example 1 in which the fine particles (C) were not used, and in Comparative Example 2 in which the fine particles (C) had a zeta potential exceeding −5 mV and a large PAST, the 15 μm line was peeled off after development. The developing adhesion was poor and the resolution was poor.

Further, Examples 1 to 4, in which NPCST or IPAST having a zeta potential of −5 mV or less as fine particles (C) are used, and the proportion of the fine particles (C) in the solid content of the photosensitive resin composition is 13% or more, In No. 6, thermal flow was suppressed. Therefore, Examples 1, 3, 4, and 6 in which an ink repellent was further blended had good ink layer uniformity after ink jetting. On the other hand, Comparative Example 1 in which the fine particles (C) were not used had poor ink layer uniformity after inkjet. Further, Comparative Example 2 using PMAST having a zeta potential exceeding −5 mV as the fine particles (C) has a slight thermal flow despite the high content of the fine particles (C) as 22.1%. Ink layer flatness after inkjet was also poor compared to Examples 1, 3, 4, and 6.

Since the photosensitive resin composition for forming a partition wall of the present invention has improved development adhesion of the partition wall, a high resolution pattern can be formed by using this. Such a partition can provide a high-resolution color filter and organic EL element.
The entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2010-283376 filed on Dec. 20, 2010 are cited here as disclosure of the specification of the present invention. Incorporated.

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Layer of photosensitive composition, 3 ... Mask, 4 ... Light, 5 ... Exposed part, 6 ... Unexposed part, 7 ... Dot, 8 ... Partition, 11 ... Ink layer x ... Ink layer thickness measurement Location (center), y1 to y4 ... Ink layer thickness measurement location (at the partition)

Claims

A photosensitive resin composition for forming a partition disposed in a form of dividing a plurality of pixels on a substrate by a photolithography method, comprising a binder resin (A) and a photoactivator (B) Fine particles (C) in a dispersion using an organic solvent as a dispersion medium and having a zeta potential of −100 to −5 mV as measured by electrophoretic light scattering of the fine particles (C) in the dispersion (C) ) And an organic solvent (D), at least part of which is an organic solvent of the dispersion.
The photosensitive resin composition according to claim 1, wherein the fine particles (C) have an average particle diameter of 5 to 100 nm.
The photosensitive property according to claim 1 or 2, wherein the dispersion medium in the dispersion liquid of the fine particles (C) is an organic solvent having an SP value of 9 to 20 (cal / cm 3 ) 1/2 having at least one hydroxyl group. Resin composition.
The photosensitive resin composition according to any one of claims 1 to 3, wherein the fine particles (C) are silica fine particles.
The photosensitive resin composition according to claim 4, wherein the silica fine particles are colloidal silica.
The photosensitive resin composition according to any one of claims 1 to 5, wherein the content of the fine particles (C) is 3 to 35 mass% with respect to the total solid content of the composition.
The photosensitive resin composition according to claim 1, further comprising a colorant (E).
The photosensitive resin composition according to claim 7, wherein the colorant (E) is at least one selected from the group consisting of carbon black, titanium black, a black metal oxide pigment, a silver tin alloy, and an organic pigment. .
The photosensitive resin composition according to any one of claims 1 to 8, wherein a partition wall forming surface of the substrate has a surface property having good affinity with an alkali developer used in the photolithography method.
10. A partition formed on a substrate in a plurality of partitions for pixel formation, and formed by a photolithography method using the photosensitive resin composition according to claim 1. A partition wall characterized by that.
11. A color filter having a plurality of pixels and a partition located between adjacent pixels on the substrate, wherein the partition is the partition according to claim 10.
An organic EL element having a plurality of pixels and a partition located between adjacent pixels on the substrate, wherein the partition is the partition according to claim 10.