KR20100061341A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE: A photosensitive resin composition is provided to have excellent applicability and ink repelling property and to be suitable for forming a lattice structure such as black matrix of a color filter by including polymerizable compound, a photopolymerization initiator, and a fluorosurfactant. CONSTITUTION: A photosensitive resin composition contains a photopolymerizable compound, a photopolymerization initiator, and a fluorosurfactant having a fluorinated alkenyl group and an amphiphilic group in a side chain. The fluorosurfactant is a polymer having an average molecular weight of 5,000~30,000. The fluorinated alkenyl group is a perfluoro alkenyl group. The fluorinated alkenyl group is marked as a chemical formula (c1-1) or (c1-2).

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition.

A display body such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which paired electrodes are formed to face each other. In addition, a color filter having a pixel region formed of each color such as red (R), green (G), and blue (B) is formed inside one substrate. In order to improve contrast, prevent light leakage, and the like, a black matrix disposed in a matrix form is formed in the color filter so as to partition pixel areas of R, G, and B colors.

A conventional color filter forms a black matrix by a lithography method, and the pattern of each color is predetermined by repeating application, exposure, and development for each photosensitive resin composition of each of R, G, and B colors in each region partitioned by the black matrix. It has been produced to form at the position of. In recent years, in order to improve productivity, the method of manufacturing a color filter by the inkjet method is examined. In this inkjet system, ink of R, G, and B colors is discharged from the inkjet nozzles in respective regions partitioned by the formed black matrix, and the collected ink is cured by heat or light to produce a color filter.

By the way, the photosensitive resin composition used for forming a black matrix in this inkjet method is a so-called solvent-based solvent for ink solvents such as water and xylene to prevent mixing of ink between adjacent pixel regions and the like. Ink repellency is calculated | required.

As the photosensitive resin composition having such ink repellency, a polymerized unit and an ethylenic group having at least one alkyl group having 20 or less carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (wherein the alkyl group includes an etheric oxygen atom). The negative photosensitive resin composition (patent document 1) etc. which contained the ink repellent agent which consists of a polymer which has a polymer unit which has a double bond are proposed. In this negative photosensitive resin composition, ink repellency can be acquired by the ink repellent fluorinated alkyl group. Moreover, since an ink repellent agent has the polymer unit which has an ethylenic double bond, it hardens | cures by light irradiation and ink repellency persists.

Patent Document 1: International Publication No. 2004/042474 Pamphlet

However, although the negative photosensitive resin composition described in patent document 1 can exhibit the outstanding ink repellency, there exists a problem in applicability | paintability. MEANS TO SOLVE THE PROBLEM In order to improve applicability | painting, the present inventors thought about adding surfactant which is considered effective for improving applicability | paintability. Then, when the photosensitive resin composition which substituted the ink repellent agent with the perfluoro alkyl group containing fluorine-type surfactant was developed, applicability | paintability improved but it turned out that there was a problem in ink repellency.

This invention is made | formed in view of the above subject, and an object of this invention is to provide the photosensitive resin composition which has outstanding coating property and outstanding ink repellency.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved by using the fluorine-type surfactant which has a specific structure, and came to complete this invention. Specifically, the present invention provides the following.

The photosensitive resin composition containing a photopolymerizable compound (A), a photoinitiator (B), and a fluorine-type surfactant (C), The said fluorine-type surfactant (C) has a photosensitive resin composition which has a fluorinated alkenyl group and a lipophilic group in a side chain. to be.

The photosensitive resin composition which concerns on this invention has the outstanding applicability | paintability and the outstanding ink repellency. For this reason, it is suitable to use when forming the structure (lattice-shaped structure) represented by the black matrix of a color filter, for example.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.

The photosensitive resin composition which concerns on this invention contains a photopolymerizable compound (A), a photoinitiator (B), and a fluorine-type surfactant (C). Hereinafter, each component is demonstrated.

[Photopolymerizable compound (A)]

The photopolymerizable compound (A) is a substance which is polymerized by being irradiated with light such as ultraviolet rays and cured. As a photopolymerizable compound (A), resin or monomer which has an ethylenically unsaturated group is preferable, and it is more preferable to combine these. By combining the resin which has an ethylenically unsaturated group, and the monomer which has an ethylenically unsaturated group, hardenability can be improved and pattern formation can be made easy. In the present specification, among the compounds having an ethylenically unsaturated group, those having a weight average molecular weight of 1,000 or more are referred to as "resins having an ethylenically unsaturated group", and those having a weight average molecular weight of less than 1,000 are referred to as "monomers having an ethylenically unsaturated group". .

≪Resin having an ethylenically unsaturated group≫

Examples of the resin having an ethylenically unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumaric acid, monoethyl fumaric acid, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, and ethylene glycol Monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth Acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) arc Rate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( Oligomers polymerized by meta) acrylate, 1,6-hexanediol di (meth) acrylate, cardo epoxy diacrylate, etc .; polyester prepolymers obtained by condensation of polyhydric alcohols with monobasic or polybasic acids Polyurethane (meth) acrylate obtained by making (meth) acrylic acid react after making polyester (meth) acrylate and polyol and the compound which has two isocyanate groups react by making it react (meth) acrylic acid; Bisphenol-A epoxy Resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy Epoxy resins such as resins, resol type epoxy resins, triphenolmethane type epoxy resins, polycarboxylic acid polyglycidyl esters, polyol polyglycidyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, and dihydroxy benzene type epoxy resins. Epoxy (meth) acrylate resin etc. which are obtained by making resin and (meth) acrylic acid react are mentioned. Moreover, resin which made polybasic acid anhydride react with epoxy (meth) acrylate resin can be used.

Moreover, as resin which has an ethylenically unsaturated group, resin obtained by making the reaction material of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) further react with polybasic acid anhydride (a3) can be used preferably.

<Epoxy compound (a1)>

Examples of the epoxy compound (a1) include glycidyl ether type, glycidyl ester type, glycidyl amine type, alicyclic type, bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, naphthalene type, fluorene type, Phenol novolak-type orthocresol type epoxy resin etc. are mentioned. Especially, a biphenyl type epoxy resin is preferable. The biphenyl type epoxy resin has one or more biphenyl skeleton represented by following formula (a1-1) in a principal chain, and has one or more epoxy groups. Moreover, it is preferable to have two or more epoxy groups as an epoxy compound (a1). This epoxy compound (a1) can be used individually or in combination of 2 or more types.

In Formula (a1-1), some R <^1a> respectively independently represents a hydrogen atom, a C1-C12 alkyl group, a halogen atom, or the phenyl group which may have a substituent, and l represents the integer of 1-4.

Of the biphenyl type epoxy resins, epoxy resins represented by the following formula (a1-2) are preferably used, and epoxy resins represented by the following formula (a1-3) are particularly preferably used. By using the epoxy resin of Formula (a1-3), the balance of sensitivity and solubility is excellent, and also the photosensitive resin composition excellent in the sharpness and adhesiveness of a pixel edge can be obtained.

In Formulas (a1-2) and (a1-3), a plurality of R ^{2a 's} each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom or a phenyl group which may have a substituent, and p is an integer of 1 to 4 Indicates. q represents the number of 0-10 as an average value, and it is preferable that it is less than one.

Moreover, the epoxy resin represented by a following formula (a1-4) among biphenyl type epoxy resins is also used preferably. By using the epoxy resin of Formula (a1-4), the balance of sensitivity and solubility is excellent, and the photosensitive resin composition excellent in the sharpness and adhesiveness of a pixel edge can be obtained further.

In Formula (a1-4), a plurality of R ^{3a 's} each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom or a phenyl group which may have a substituent. r represents the number of 0-10 as an average value, and it is preferable that it is less than one.

<Ethylenic unsaturated group containing carboxylic acid compound (a2)>

As an ethylenically unsaturated group containing carboxylic acid compound (a2), the monocarboxylic acid compound containing reactive ethylenic double bonds, such as an acryl group and a methacryl group, is preferable in a molecule | numerator. Acrylic acid, methacrylic acid, (beta) -styryl acrylic acid, (beta) -furfuryl acrylic acid, (alpha)-cyanocinnamic acid, cinnamic acid etc. are mentioned as such an ethylenically unsaturated group containing carboxylic acid compound. This ethylenically unsaturated group containing carboxylic acid compound (a2) can be used individually or in combination of 2 or more types.

A well-known method can be used as a method of making an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) react. For example, a tertiary amine such as triethylamine and benzylethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, The method of making it react for several to several tens hours at the reaction temperature of 50-150 degreeC in an organic solvent using quaternary ammonium salts, such as benzyl triethylammonium chloride, pyridine, triphenylphosphine, as a catalyst.

The usage-amount ratio in reaction of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) is a ratio of the epoxy equivalent of an epoxy compound (a1) and the carboxylic acid equivalent of an ethylenically unsaturated group containing carboxylic acid compound (a2), and is 1 normally. : 0.5-1: 2, Preferably it is 1: 0.8-1: 25, More preferably, it is 1: 1. Since it exists in the tendency for crosslinking efficiency to improve by setting it as the said range, it is preferable.

<Polybasic acid anhydride (a3)>

The polybasic acid anhydride (a3) includes a compound having at least two benzene rings as an anhydride of a carboxylic acid having two or more carboxyl groups. As such polybasic acid anhydride (a3), for example, an acid anhydride having a biphenyl skeleton as represented by the following formula (a3-1), and two benzene rings as represented by the following formula (a3-2) are bonded to an organic group. Acid anhydrides.

R <^4a> shows the alkylene group which may have a C1-C10 substituent in a formula (a3-2).

By using anhydrides of carboxylic acids having two or more carboxyl groups, at least two benzene rings can be introduced into the photopolymerizable compound (A).

Moreover, polybasic acid anhydride (a3) may contain other polybasic acid anhydride other than the acid anhydride which has at least two said benzene rings. Other polybasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, and the like. Pyromellitic acid, benzophenonetetracarboxylic acid dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3- Methyl tetrahydro phthalic anhydride, 4-methyl tetrahydro phthalic anhydride, 3-ethyl tetrahydro phthalic anhydride, 4-ethyl tetrahydro phthalic anhydride is mentioned. These polybasic acid anhydrides can be used individually or in combination of 2 or more types.

After reacting an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2), a well-known method can be used as a method of making a polybasic acid anhydride (a3) react further. In addition, the usage-amount ratio is the ratio of the number-of-moles of OH group in the reaction material of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2), and the acid anhydride group of polybasic acid anhydride (a3), and is usually 1: 1: 1: 0.1. Preferably it is 1: 0.8-1: 0.2. It exists in the tendency for the solubility to a developing solution to become suitable by setting it as the said range, and it is preferable.

The acid value of the resin obtained by further reacting the reaction product of the epoxy compound (a1) and the ethylenically unsaturated group-containing carboxylic acid compound (a2) with the polybasic anhydride (a3) is preferably 10 to 150 mgKOH / g in terms of resin solid content. More preferably, it is 70-110 mgKOH / g. By making the acid value of resin into 10 mgKOH / g or more, sufficient solubility to a developing solution can be obtained, and by setting it to 150 mgKOH / g or less, sufficient hardenability can be obtained and surface quality can be made favorable.

Moreover, it is preferable that the weight average molecular weights of resin are 1,000-40,000, More preferably, it is 2,000-30,000. By setting the weight average molecular weight to 1,000 or more, heat resistance and film strength can be improved, and by setting it as 40,000 or less, sufficient solubility in a developer can be obtained.

Moreover, as resin which has an ethylenically unsaturated group, resin which has a cardo structure in a molecule | numerator can be used preferably. Since resin which has a cardo structure has high heat resistance and chemical-resistance, it can improve the heat resistance and chemical-resistance of the photosensitive resin composition by using it for a photopolymerizable compound (A). For example, resin represented by a following formula (a4-1) can be used preferably.

In formula (a4-1), X is group represented by a following formula (a4-2).

In the formula (a4-1), Y represents maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chloric anhydride, and methyl tetra It is a residue remove | excluding the carboxylic anhydride group (-CO-O-CO-) from dicarboxylic acid anhydrides, such as hydrophthalic anhydride and glutaric anhydride.

Moreover, in Formula (a4-1), Z removes two carboxylic anhydride groups from tetracarboxylic dianhydride, such as pyromellitic anhydride, a benzophenone tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride, and a biphenyl ether tetracarboxylic dianhydride. Residue.

In addition, in Formula (a4-1), s is an integer of 0-20.

<< monomer having an ethylenically unsaturated group >>

As a monomer which has an ethylenically unsaturated group, there exist a monofunctional monomer and a polyfunctional monomer.

Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy Methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, sheet Laconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate 2-phenoxy-2-hydroxypropyl (meth) a Acrylate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl ( Meta) acrylates, 2,2,2-trifluoroethyl (meth) acrylates, 2,2,3,3-tetrafluoropropyl (meth) acrylates, and half (meth) acrylates of phthalic acid derivatives; Can be mentioned. These monofunctional monomers can be used individually or in combination of 2 or more types.

On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di ( Meta) acrylate, butylene glycol di (meth) acrylate, neopentylglycol di (meth) acrylate, 1,6-hexaglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipene Taerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2 -Hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid Diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie tolylene diisocyanate), trimethylhexamethylene diisocyanate Reactant of 2-hydroxyethyl (meth) acrylate with hexamethylene diisocyanate and the like, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol (meth) acrylamide Of the condensation product, such as and the like functional monomer or triacrylate formal. These polyfunctional monomers can be used individually or in combination of 2 or more types.

It is preferable that content of the monomer which has this ethylenically unsaturated group is 5-50 weight% with respect to solid content of the photosensitive resin composition, More preferably, it is the range of 10-40 weight%. By setting it as the said range, it exists in the tendency to balance the sensitivity, developability, and resolution, and is preferable.

It is preferable that content of a photopolymerizable compound (A) is 5-50 weight% with respect to solid content of the photosensitive resin composition, More preferably, it is the range of 10-40 weight%. By setting it as the said range, it exists in the tendency to balance the sensitivity, developability, and resolution, and it is preferable.

[Photopolymerization Initiator (B)]

Examples of the photopolymerization initiator (B) include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2. -Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)- 2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone-1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 2,4,6-trimethylbenzoyl diphenylphosphineoxide, 4- Benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoate butyl, 4-dimethylamino-2-ethylhexylbenzoic acid, 4- Dimethylamino-2-isoamylbenzoic acid, benzyl-β-methok Ethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chloroti Oxanthone, 2,4-dimethyl thioxanthone, 1-chloro-4-propoxy city oxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthiooxane Ten, 2-isopropyl thioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene Peroxide, 2-mercaptobenzoimidal, 2-mercaptobenzooxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imida Zolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3- Dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, ben Join isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, Dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4 -Phenoxyacetophenone, thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, dibenzosuberon, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7- Bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2, 4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine , 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-meth Methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6 -(3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s- Triazine etc. are mentioned. Especially, it is especially preferable in terms of a sensitivity to use an oxime photoinitiator. These photoinitiators can be used individually or in combination of 2 or more types.

It is preferable that content of a photoinitiator (B) is 0.5-30 weight% with respect to solid content of the photosensitive resin composition, More preferably, it is the range of 1-20 weight%. By setting it as the said range, sufficient heat resistance and chemical-resistance can be obtained, and the film formation ability can be improved and a photocuring defect can be suppressed.

[Fluorinated Surfactant (C)]

The fluorine-type surfactant (C) contained in the photosensitive resin composition which concerns on this invention is a polymer which has a fluorinated alkenyl group and a lipophilic group in a side chain.

When the fluorine-based surfactant (C) contains a fluorinated alkenyl group, it exhibits high liquid repellency as compared with the case where a fluorinated alkyl group is included.

2-20 are preferable and, as for carbon number of the fluorinated alkenyl group, it is more preferable that it is a C6-C10 fluorinated alkenyl group (it shall contain a trans body and a cis body.). Specifically, a perfluoro-2-hexen-2-yl group, a perfluoro-2-hepten-2-yl group, a perfluoro- (2-, 3- or 4-) octene-2-yl group, a perfluoro Rho- (2-, 3- or 4-) nonen-2-yl group, perfluoro- (2-, 3- or 4-) decen-2-yl group, perfluoro-2-ethyl-1-butene- 1-yl group, perfluoro-4-methyl-3-isopropyl-2-penten-2-yl group, perfluoro (2-isopropyl-1,3-dimethyl-1-butenyl) group, perfluoro (1-ethyl-2-methyl-1-propenyl) group, perfluoro-2-methyl-2-penten-3-yl group, etc. are mentioned.

Among these, a branched chain is more preferable. By branching, liquid repellency improves. In addition, about the ratio of fluorination, it is preferable that 25% or more of the hydrogen atoms in an alkenyl group are substituted by the fluorine atom, It is preferable that 50% or more are substituted by the fluorine atom, The perfluoro egg in which all the hydrogen atoms were substituted by the fluorine atom. It is especially preferable that it is a kenyl group.

Among such fluorinated alkenyl groups, those represented by the following (c1-1) or (c1-2) are particularly preferable.

As a monomer containing such a fluorinated alkenyl group, the monomer represented by following formula (c1-3) (henceforth "monomer (c1)") is preferable. When the fluorine-based surfactant (C) is a polymer having such a monomer (c1) as a repeating unit, high ink repellency can be exhibited.

In formula (c1-3), R ^1c represents a hydrogen atom or a methyl group, and Rf represents the fluorinated alkenyl group described above. R ^2c represents an alkylene group having 1 to 10 carbon atoms, and may be linear or branched.

Examples of the hydrophilic group include those contained in conventionally known nonionic surfactants, but preferably include alkylene groups interrupted by ether bonds, ester bonds or carbonyl groups. Especially, it is preferable that polyalkyleneoxy group (polyethyleneoxy group, polypropyleneoxy group, polybutyleneoxy group etc.) is included.

The fluorine-based surfactant (C) can be obtained by polymerizing at least the monomer having the fluorinated alkenyl group and the monomer having the lipophilic group. As a monomer which has a lipophilic group, the monomer (henceforth "monomer (c2)") which has a structure represented by an ethylenically unsaturated group and a following formula (c2-1) is preferable.

It is more preferable that this monomer (c2) has a structure represented by an ethylenically unsaturated group and following formula (c2-2).

R <^3c> may represent a C1-C5 alkylene group in formula (c2-1) and (c2-2), and may be linear or branched. Especially, a C1-C3 alkylene group is preferable and an ethylene group is the most preferable. R <^4c> represents a C1-C20 alkyl group which may have a hydrogen atom, a hydroxyl group, or a substituent, and may be linear or branched. Especially, a C1-C3 alkyl group is preferable and a methyl group is the most preferable. As said substituent, a carboxyl group, a hydroxyl group, a C1-C5 alkoxy group, etc. are mentioned. x represents an integer greater than or equal to 1, the integer of 1-60 is preferable, and the integer of 1-12 is more preferable.

As such a monomer (c2), the compound etc. which are represented by following formula (c2-3) are mentioned. These monomers (c2) can be used individually or in combination of 2 or more types.

R <^5c> represents a hydrogen atom or a methyl group in formula (c2-3). R <^3c> , R <^4c> , and x are the same as said Formula (c2-1), (c2-2).

The molar ratio of the fluorinated alkenyl group and the lipophilic group in the fluorine-based surfactant (C), that is, the molar ratio of the monomer (c1) having the fluorinated alkenyl group and the monomer (c2) having the lipophilic group is preferably 1:99 to 50:50. , 1:99 to 25:75 are more preferable, and 5:95 to 25:75 are the most preferable.

Among these, the fluorine-type surfactant which superposed | polymerized the monomer (c1) whose said Rf is a perfluoro alkenyl group in the said Formula (c1-3), and the said monomer (c2) is preferable, and the specific example is a futagent 730FL (the said Formula ( Acrylic monomer in which Rf is represented by said Formula (c1-1) in c1-3): Acrylic monomer which has an ethylene oxide group in said Formula (c2-3) = 3:97 (molar ratio)), Futagent 710FL (The said Formula. Acrylic monomer in which Rf is represented by said Formula (c1-1) in (c1-3): Acrylic monomer which has an ethylene oxide group in said Formula (c2-3) = 9: 91 (molar ratio)), Futagent 703FL (the said Acrylic monomer in which Rf is represented by said Formula (c1-1) in Formula (c1-3): Acrylic monomer (c1) which has an ethylene oxide group in said Formula (c2-3) = 25:75 (molar ratio)) (all Neos Co., Ltd.) etc. are mentioned.

The fluorine-based surfactant (C) may be any of a random polymer, a block polymer and a graft polymer, but is preferably a graft polymer. By setting it as a graft polymer, applicability | paintability can be improved more, maintaining compatibility with a photopolymerizable compound (A). Moreover, in the case of a graft polymer, even if it increases content, there is little fear of turbidity.

5,000-30,000 are preferable and, as for the weight average molecular weight of this fluorine-type surfactant (C), 10,000-20,000 are more preferable. Moreover, it is preferable that it is 1,000-20,000 weight ppm with respect to a photopolymerizable compound (A), and, as for content of a fluorine-type surfactant (C), it is more preferable that it is 2,000-8,000 weight ppm. The photosensitive resin layer excellent in ink repellency can be obtained even in a small addition amount like the said range.

Moreover, the photosensitive resin composition which concerns on this invention may contain the other conventionally well-known surfactant in the range which does not impair the effect of this invention.

[Colorant (D)]

The photosensitive resin composition concerning this invention may contain a coloring agent. As a coloring agent (D), light-shielding agents, such as carbon black and titanium black, are mentioned. Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si, Al, etc. Inorganic pigments such as various metal oxides, complex oxides, metal sulfides, metal sulfates, or metal carbonates.

As carbon black, well-known carbon black, such as channel black, furnace black, thermal black, and lamp black, can be used, but channel black can be suitably used because of its excellent light shielding properties. Moreover, resin coated carbon black can also be used. Specifically, a resin-coated carbon black obtained by mixing a carbon black with a resin having reactivity with a carboxyl group, a hydroxyl group, a carbonyl group present on the surface of the carbon black, and heating at 50 to 380 degrees, or a water-organic solvent mixture system or a water-interface The resin coating carbon black etc. which were obtained by disperse | distributing an ethylenic monomer to an activator mixture system, and carrying out radical polymerization or radical copolymerization in presence of a polymerization initiator are mentioned. Since the resin-coated carbon black has lower conductivity than carbon black without resin coating, when used as a color filter such as a liquid crystal display, leakage of current is small and a high power consumption display with high reliability can be formed.

You may add an organic pigment as an auxiliary pigment to the said inorganic pigment as a coloring agent. Organic pigments can be obtained by appropriately selecting and adding those complementary to the inorganic pigments. For example, carbon black has a reddish black color. Therefore, the addition of the blue-pigmented organic pigment, which is a red complementary color, to the carbon black causes the redness of the carbon black to disappear, thereby making the overall black more desirable. It is preferable to use an organic pigment in 10 to 80 weight% with respect to the sum total of an inorganic pigment and an organic pigment, More preferably, it is 20 to 60 weight%, More preferably, it is the range of 20 to 40 weight%.

As the inorganic pigment and the organic pigment, a solution obtained by dispersing the pigment at an appropriate concentration using a dispersant may be used. For example, as the inorganic pigment, carbon dispersion CF black (containing 20% carbon concentration) manufactured by Mikuni Dyestuff Co., Ltd. carbon dispersion CF black (containing 24% high resistance carbon) manufactured by Mikuni Dyestuff Co., Ltd. and titanium black dispersion CF black manufactured by Mikuni Dyestuff Co., Ltd. (Containing 20% of black titanium pigment). Moreover, as an organic pigment, blue pigment dispersion liquid CF blue (20% of blue pigment containing) made by Mikuni dye company, violet pigment dispersion liquid (containing 10% of violet pigment) made by Mikuni dye company, etc. are mentioned, for example. As the dispersant, a polymer dispersant of polyethyleneimine, urethane resin or acrylic resin is preferably used.

It is preferable that content of a coloring agent (D) is 10 to 70 weight% with respect to solid content of the photosensitive resin composition. By making content into 70 weight% or less, the photocuring defect can be suppressed, and by making it into 10 weight% or more, sufficient light-shielding property can be obtained. In addition, it is preferable to adjust the density | concentration of a coloring agent so that OD (Optical Density) value per 1 micrometer of film thickness may be 1.5 or more, when forming a black matrix using the photosensitive resin composition of this invention as mentioned later. When the OD value per film thickness of 1 µm is 1.5 or more, sufficient contrast can be obtained when used for the black matrix of the liquid crystal display.

[Solvent (S)]

It is preferable that the photosensitive resin composition which concerns on this invention contains the solvent for dilution. As this solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tri (Poly) such as propylene glycol monomethyl ether and tripropylene glycol monoethyl ether Ethylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (Poly) alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, cyclohexanone Ketones such as, 2-heptanone and 3-heptanone; lactic acid alkyl esters such as 2-hydroxypropionate methyl and 2-hydroxyethyl propionate; ethyl 2-hydroxy-2-methylpropionate and 3-methoxypropionic acid Methyl, 3-methoxypropionate, 3-ethoxypropionic acid Methyl, 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3 Methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, Other esters such as ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; toluene Aromatic hydrocarbons such as xylene, and amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide. These solvents can be used individually or in combination of 2 or more types.

It is preferable that content of a solvent (S) is 50-500 weight part with respect to 100 weight part of solid content of the photosensitive resin composition.

[Other Ingredients]

The photosensitive resin composition which concerns on this invention can be made to contain an additive as needed. Examples of the additive include a thermal polymerization inhibitor, an antifoaming agent, a sensitizer, a curing accelerator, a photocrosslinker, a photosensitizer, a dispersant, a dispersing aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomerating agent.

[Preparation Method of Photosensitive Resin Composition]

The photosensitive resin composition which concerns on this invention can be obtained by mixing each said component with a stirrer. Moreover, you may filter using a filter so that the obtained mixture may become uniform.

[Application Example of Photosensitive Resin Composition According to the Present Invention]

As mentioned above, the photosensitive resin composition concerning this invention is suitable for use at the time of formation of the structure (lattice-shaped structure) represented by the black matrix of a color filter, for example in order to combine outstanding applicability and outstanding ink repellency. Therefore, it describes below about the manufacturing method of the color filter using the photosensitive resin composition which concerns on this invention as an application example.

[Production method of color filter]

First, the photosensitive resin composition which concerns on this invention is apply | coated on a board | substrate using non-contact type coating apparatuses, such as a contact transfer type | mold coating apparatus, such as a roll coater, a reverse coater, and a bar coater, a spinner (rotary coating apparatus), and a curtain flow coater. As the substrate, a substrate having light transparency is used.

Next, the applied photosensitive resin composition is dried to form a coating film. The drying method is not particularly limited, and for example, (1) a method of drying for 60 to 120 seconds at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C on a hot plate, and (2) several hours to several days at room temperature. You may use the method of (3) the method of removing the solvent in the warm air heater or an infrared heater for several to ten minutes-several hours.

Subsequently, this coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. Although the energy dose to irradiate changes with the composition of the photosensitive resin composition, about 30-2,000mJ / cm <2> is preferable, for example.

Subsequently, the film | membrane after exposure is developed with a developing solution, and patterned in a desired shape. The image development method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. Examples of the developing solution include organic compounds such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Then, post-baking is performed about the pattern after image development at about 200 degreeC. At this time, it is preferable to expose the formed pattern to the whole surface. As described above, a black matrix having a predetermined pattern shape can be formed.

Subsequently, in each of the regions partitioned by the black matrix, inks of R, G, and B colors are discharged from the inkjet nozzles, and the collected ink is cured with heat or light. Thereby, a color filter can be manufactured.

Example

Hereinafter, with reference to the embodiment of the present invention will be described in detail. In addition, this invention is not limited to a following example at all.

<Example 1>

As the photopolymerizable compound (A), dipentaerythritol hexaacrylate (DPHA) was used as the following resin (A-1) and monomer (A-2). The synthesis | combining method of resin (A-1) is as follows.

[Synthesis of Resin (A-1)]

235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid were blown at a rate of 25 ml / min. It melt | dissolved by heating at 100 degreeC from 90 degreeC, blowing, and warming up to 120 degreeC slowly. During this time, the stirring was continued for about 12 hours until the acid value was measured and became less than 1.0 mgKOH / g. And it cooled to room temperature and obtained the colorless transparent solid bisphenol fluorene type epoxy acrylate.

Subsequently, 350 g of propylene glycol monomethyl ether acetate (PGMEA) was added to and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate obtained, followed by dissolving 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide. It was made to react at -115 degreeC for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain a resin (A-1). In addition, the disappearance of the acid anhydride group was confirmed by IR spectrum. The obtained resin (A-1) had a weight average molecular weight of 5,000 as measured by GPC, and had an acid value of 80 mgKOH / g. This resin (A-1) was adjusted to 55 weight% of solid content concentration in 3-methoxybutyl acetate.

As a photoinitiator (B), CGI242 (B-1, Chiba Specialty Chemical Co., Ltd.) was used.

As surfactant (C), an acryl monomer in which Rf is represented by the above formula (c1-3) in futagent 710FL (C-1, formula (c1-3): has an ethylene oxide group in formula (c2-3). Acrylic monomer = 9:91 (molar ratio) polymer, the weight average molecular weight 20,000) was used.

As the coloring agent (D), a black pigment (D-1, manufactured by Mikuni Dyestuff Co., Ltd., CF black: 25% by weight carbon black, solvent: 3-methoxybutyl acetate) was used.

As said solvent (S), the mixed solvent (S-1) of 3-methoxybutyl acetate: cyclohexanone = 60: 40 (weight ratio) was used.

Each said component and solvent were mix | blended so that the total solid content concentration might be 22 weight%, and it mixed with the stirrer for 2 hours, and filtered with a 5 micrometer membrane filter, and prepared the photosensitive resin composition. The compounding quantity of each component and a solvent is as showing in Table 1.

<Examples 2 and 3, Comparative Examples 1 and 2>

It changed to the composition of the base material in following Table 1, and prepared the photosensitive resin composition. The synthesis method of resin (A-3) in Table 1 is as follows.

[Synthesis of Resin (A-3)]

400 g of Epicoat YX4000H (manufactured by Japan Epoxy Resin, Epoxy Equivalent 192), 4 g of triphenyl phosphine, 153 g of acrylic acid, and 600 g of 3-methoxybutyl acetate were mixed and reacted at 90 to 100 ° C. Thereafter, 40 g of tetrahydrophthalic anhydride and 360 g of biphenyltetracarboxylic dianhydride were added as the polybasic acid anhydride, and further reacted to obtain a resin (A-3) having a biphenyl skeleton. The weight average molecular weight of this resin (A-3) measured by GPC was 7,000, and the acid value was 90 mgKOH / g. In addition, this resin (A-3) was adjusted to 50 weight% of solid content concentration in 3-methoxybutyl acetate.

In Table 1, the surfactant (C-2) is KL-600 (a fluorine-based surfactant having a perfluorooctylethyl (meth) acrylate-containing polymer, manufactured by Kyoeisha Chemical Co., Ltd.), and is a surfactant (C-3). Is BYK-310 (BYK Chemical Japan make, silicone type surfactant).

<Evaluation>

After apply | coating the photosensitive resin composition prepared by the said Examples 1-3 and Comparative Examples 1-2, respectively on a glass substrate, it dried at 90 degreeC for 2 minutes, and obtained the photosensitive layer which has a film thickness of about 2 micrometers. Subsequently, the photosensitive layer was irradiated with ultraviolet rays selectively at an exposure dose of 200 mJ / cm ² through a negative mask, and was 25 ° C using a solution of N-a3K (manufactured by Tokyooka Industry Co., Ltd.): pure water = 1:25 as a developer. The pattern was formed by spray-developing for 60 seconds with a furnace. Thereafter, the formed pattern was subjected to post-baking at 220 ° C. for 30 minutes to form a grid-shaped black matrix pattern having a line width of 20 μm. Then, the solvent contact angle on the pattern was diethylene glycol monobutyl ether acetate (BDGAC), diethylene glycol monoethyl ether acetate (EDGAC), 1,3-butylene glycol diacetate (1,3-BGDA), and propylene. Measurements were made on glycol monomethyl ether (PM) and pure water. The results are shown in Table 1.

TABLE 1

From Table 1, perfluoroalkyl group-containing surfactants (Comparative Example 1) and silicone-based surfactants (Comparative Example 2) were used by using a fluorine-based surfactant having a fluorinated alkenyl group and a lipophilic group in the side chain (Examples 1 to 3). It was found that excellent liquid repellency can be obtained as compared with the use case.

Claims (8)

As a photosensitive resin composition containing a photopolymerizable compound (A), a photoinitiator (B), and a fluorine-type surfactant (C), The said fluorochemical surfactant (C) has a photosensitive resin composition which has a fluorinated alkenyl group and a lipophilic group in a side chain. The method according to claim 1, The said fluorine-type surfactant (C) is a photosensitive resin composition which is a polymer of the weight average molecular weights 5,000-30,000. The method according to claim 1, The photosensitive resin composition whose said fluorinated alkenyl group is a perfluoro alkenyl group. The method according to claim 1, The photosensitive resin composition whose said fluorinated alkenyl group is branched. The method according to claim 1, The photosensitive resin composition in which the said fluorinated alkenyl group is represented by following formula (c1-1) or (c1-2).

The method according to claim 1, The photosensitive resin composition whose molar ratio of the said fluorinated alkenyl group and the said lipophilic group is 1: 99-50: 50. The method according to claim 1, The photosensitive resin composition whose content with respect to the said photopolymerizable compound (A) of the said fluorine-type surfactant (C) is 1,000-20,000 weight ppm. The method according to claim 1, Furthermore, the photosensitive resin composition containing a coloring agent (D).