JP2007071994A - Black photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a black photosensitive resin composition forming an insulating film, and to further provide a black photosensitive resin composition forming a film which takes on a more desirable black color and gives a more preferable pattern shape. <P>SOLUTION: In the black photosensitive resin composition containing a pigment component that contains black pigment, the pigment component comprises an insulating organic pigment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a black photosensitive resin composition suitable for producing a color filter such as a liquid crystal display or a black matrix.

  The black photosensitive resin composition is an indispensable material for manufacturing display elements such as a color filter, a liquid crystal display material, and an organic electroluminescence (EL) display panel material. For example, a color filter provided in various multicolor displays such as a color liquid crystal display has a boundary between colored layers such as R (red), G (green), and B (blue) in order to enhance display contrast and coloring effect. A black matrix is required for the portion, and this black matrix is formed from a black photosensitive resin composition.

  Regarding the black matrix, the following documents exist. Patent Document 1 discloses a black matrix material containing cobalt oxides as a black pigment in order to obtain a black matrix having high blackness and insulating properties. In Patent Document 2, the erosion rate of the formed pattern is small, the pattern shape hardly forms a reverse taper at the time of development, and it is possible to effectively prevent the rubbing cloth from being caught on the pattern portion and peeling of the pattern, and to be seized. It is disclosed that it is used for forming a spacer and / or a black matrix on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device that does not cause display defects such as the above. Patent Document 3 discloses a black matrix material using a perylene-based compound. Patent Document 4 discloses a black matrix material including an insulating organic pigment composed of a mixed-colored organic pigment that has been pseudo-blackened and a light shielding material such as carbon black in order to form a highly insulating light shielding film having a high light shielding rate. Has been.

  In recent years, there are cases where a black matrix material is used as a photospacer for indicating between electrode substrates present with a liquid crystal layer interposed therebetween. In this case, the photo spacer is required to have insulating properties. In the field related to liquid crystal panels, there is a technique for increasing image contrast using a black photo spacer instead of a bead spacer.

In the case of the organic EL panel element, an insulating layer is also required between the pixels. In the field related to the organic EL panel, there is a technique for improving the light shielding property by forming a black lattice (black matrix).
JP 2002-47423 A JP 2002-36595 A JP-A-6-289602 Japanese Patent No. 2552391

  However, the current mainstream carbon pigment-dispersed photosensitive compositions have a low electrical resistance, and thus are difficult to use as photo spacers or insulating materials. Therefore, the insulating property of the black matrix material using an inorganic compound having a smaller electric resistance than the organic compound as in Patent Documents 1 to 4 is insufficient. In Patent Documents 3 and 4, perylene black is used as the black organic pigment, but other than this, for example, an inorganic compound such as carbon black is included, and the insulating property is insufficient.

  In addition, even if organic pigments such as red, blue, green, cyan, magenta, yellow, and pink are used, the visible light is not sufficiently shielded, and the total pigment content in the pigment-dispersed photosensitive composition must be increased. was there. However, since the ratio of the pigment to the pigment-dispersed photosensitive resin is relatively increased, the sensitivity and developability are remarkably deteriorated, a satisfactory black matrix pattern shape cannot be obtained, and the contrast can be improved. could not.

  In view of the above problems, the present invention provides a black photosensitive resin composition that forms a film having insulating properties, and further exhibits a more preferable black color and forms a film having a good pattern shape. I will provide a.

The black photosensitive resin composition containing the pigment component containing the black pigment according to the present invention is characterized in that the pigment component is composed of an insulating organic pigment.
By comprising in this way, the film | membrane formed with the said black photosensitive resin composition can make insulation.

The black pigment of the black photosensitive resin composition according to the present invention is perylene black.
By comprising in this way, since the insulating organic material can be used without using the conductive inorganic compound, the film formed of the black photosensitive resin composition may be insulative. it can.

The pigment component of the black photosensitive resin composition according to the present invention includes a red organic pigment and a blue organic pigment.
By comprising in this way, the black degree which the pigment component containing a black pigment exhibits can be improved, and contrast can be improved.

Moreover, the dielectric constant of the film formed with the black photosensitive resin composition concerning this invention is 7 or less, It is characterized by the above-mentioned.
With this configuration, insulation at a practical level can be obtained.

Moreover, the optical density of the film formed of the black photosensitive resin composition according to the present invention is 1 or more per 1 μm of film thickness.
By comprising in this way, the film | membrane formed with the said black photosensitive resin composition has high light-shielding property.

Moreover, the said black photosensitive resin composition concerning this invention is characterized by including a photopolymerizable compound, a photoinitiator, and a solvent.
By comprising in this way, a negative type black photosensitive resin composition can be obtained.

  The ratio of the pigment component of 20% by weight to 250% by weight based on the total weight of the photopolymerizable compound, the photopolymerization initiator, and the solvent contained in the black photosensitive resin composition according to the present invention. It is included in.

By comprising in this way, the optimal light-shielding rate and pattern shape can be obtained within the range of this weight ratio.
Moreover, a black matrix is formed from the black photosensitive resin composition of the present invention.

With this configuration, a high contrast can be obtained.
The black matrix is used for an organic electroluminescence (EL) display panel.

By comprising in this way, the organic electroluminescent display which has high contrast can be obtained.
The black matrix may be used for a liquid crystal display panel.

By comprising in this way, the liquid crystal display panel which has high contrast can be obtained.
Moreover, a photo spacer is formed from the black photosensitive resin composition of the present invention.

By comprising in this way, the film | membrane formed with the black photosensitive resin composition can be used as a photospacer.
Further, the photo spacer is used for a liquid crystal display panel.

  By comprising in this way, the liquid crystal display panel using the film | membrane formed with the black photosensitive resin composition as a photospacer can be obtained.

  By using the present invention, a black photosensitive resin film having high insulating properties can be formed. Moreover, the black photosensitive resin film which exhibits more preferable black and has high light-shielding property can be formed.

Hereinafter, embodiments of the present invention will be described in detail.
The black photosensitive resin composition in this embodiment contains a photopolymerizable compound, a photopolymerization initiator, a pigment, and a solvent. This pigment is made of an insulating organic pigment exhibiting black without containing a conductive black pigment such as carbon black. Further, as the pigment, in addition to the insulating organic pigment, a red organic pigment and / or a blue organic pigment may be included, and an organic pigment exhibiting a color such as yellow or violet may be included.

  The black photosensitive resin composition contains the pigment component in a proportion of 20 wt% to 250 wt% with respect to the total weight of the photopolymerizable compound, the photopolymerization initiator, and the solvent. . The proportion of the pigment component can be changed in accordance with the film thickness when using a film formed from the black photosensitive resin composition and the required light shielding rate. When the pigment component ratio is less than 20% by weight, the light shielding ratio becomes extremely small. On the other hand, if the pigment component ratio exceeds 250% by weight, the cross-linked structure of the resin is reduced as a whole, sufficient sensitivity cannot be obtained during exposure, and a satisfactory pattern shape cannot be obtained.

  The photopolymerizable compound is a photopolymerizable compound that can be an alkali-soluble resin, and is represented by the following general formula (1).

However, in the said General formula (1), n is an integer of 1-20,
Y is a residue obtained by removing the acid anhydride group of the dicarboxylic acid anhydride,
Z is a residue obtained by removing the acid anhydride group of tetracarboxylic dianhydride;
X is

で表される基であり、
Ｒ_１、Ｒ_２は、Ｈ、ＣＨ_３又は

A group represented by
R ₁ and R ₂ are H, CH ₃ or

であり、
Ｒ_３は、Ｈ又はＣＨ_３である。

And
R ₃ is H or CH ₃ .

Here, the “acid anhydride group” refers to a “—CO—O—CO— group”.
Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyl Examples include tetrahydrophthalic anhydride and glutaric anhydride.
Examples of tetracarboxylic dianhydrides include aromatic polycarboxylic anhydrides such as pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride. Things.

  The photopolymerizable compound represented by the general formula (1) can be obtained by the method described in JP-A No. 2001-354735. Since the photopolymerizable compound represented by the general formula (1) has substantially no dicarboxylic anhydride residue in the polymerization chain, it differs from a compound having a dicarboxylic anhydride residue in the polymerization chain, Even at the same solid content concentration, it is easy to control the viscosity of the solution, and it is possible to improve workability during coating, improve coating characteristics, and make the film thickness uniform.

  The photopolymerizable compound represented by the general formula (1) has at least two ethylenically unsaturated double bonds capable of addition polymerization in the compound, and the photosensitive resin composition activates the photopolymerization initiator. When irradiated with light of a predetermined wavelength to be converted, even if the optical density is high, it can be cured by addition polymerization by the action of a photopolymerization initiator. In other words, when the black matrix pattern of a color filter such as a liquid crystal display is formed, if the photosensitive resin composition of the present invention is used, the content of the black pigment can be increased to improve the light shielding property. For this reason, a color filter having a high display contrast and a beautiful color of R, G, B can be manufactured.

It is preferable to add a compound having an ethylenically unsaturated double bond capable of addition polymerization to the photosensitive resin composition.
Here, “a compound having an ethylenically unsaturated double bond capable of addition polymerization” (hereinafter referred to as “ethylenic compound”) means that when the photosensitive resin composition is irradiated with light having a predetermined wavelength, A compound having at least one ethylenically unsaturated double bond that undergoes addition polymerization and curing by the action of a photopolymerization initiator, the monomer having the ethylenically unsaturated double bond, a side chain, or a main chain Is a polymer having an ethylenically unsaturated double bond. The monomer is a differentiated concept relative to a so-called polymer substance, and is not limited to a “monomer” in a narrow sense, but includes a dimer, a trimer, and an oligomer.

  Examples of the monomer include unsaturated carboxylic acids, esters of aliphatic (poly) hydroxy compounds and unsaturated carboxylic acids, esters of aromatic (poly) hydroxy compounds and unsaturated carboxylic acids, and unsaturated carboxylic acids. , Unsaturated carboxylic acid amide, unsaturated carboxylic acid nitrile obtained by esterification reaction of polycarboxylic acid with polyhydric carboxylic acid and polyhydric hydroxy compound such as aliphatic (poly) hydroxy compound and aromatic (poly) hydroxy compound described above Etc.

  Specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl Ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylic amide, methacrylic amide, acrylonitrile, methacrylonitrile, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethyl Glycol diacrylate, diethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol di Methacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentae Thritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, cardoepoxy diacrylate, cardoepoxy dimethacrylate, acrylates and methacrylates of these exemplary compounds are replaced with fumarate, maleate, crotonate, itaconate, acrylic acid, methacrylic acid, fumaric acid, maleic acid , Crotonic acid, itaconic acid, hydroquinone monoacrylate, hydroquinone monometa Acrylate, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol diacrylate, pyrogallol triacrylate, condensate of acrylic acid with phthalic acid and diethylene glycol, condensate of acrylic acid with maleic acid and diethylene glycol, Useful condensates of methacrylic acid with terephthalic acid and pentaerythritol, condensates of acrylic acid with adipic acid and butanediol with glycerin, ethylene bisacrylamide, ethylene bismethacrylamide, allyl ester of diallyl phthalate, divinyl phthalate is there.

  Examples of the polymer having an ethylenically unsaturated double bond in the side chain or main chain include, for example, a polyester obtained by polycondensation reaction of an unsaturated divalent carboxylic acid and a dihydroxy compound, an unsaturated divalent carboxylic acid, Polyamide, itaconic acid, propylidene succinic acid obtained by polycondensation reaction with diamine, polyester obtained by polycondensation reaction of ethylidene malonic acid and dihydroxy compound, itaconic acid, propylidene succinic acid, ethylidene malonic acid and diamine Polyamide obtained by polycondensation reaction, phenol novolac type epoxy acrylate, phenol novolac type epoxy methacrylate, cresol novolac type epoxy acrylate, cresol novolac type epoxy methacrylate, bisphenol A type epoxy acrylate Bisphenol S-type epoxy acrylate, urethane acrylate oligomer, and urethane methacrylate oligomer. The epoxy (meth) acrylate resin may be further reacted with a polybasic acid anhydride. Polymers having a functional group having a reactive activity such as a hydroxy group or a halogenated alkyl group in the side chain, such as polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin, and acrylic acid, methacrylic acid, fumaric acid Polymers obtained by polymer reaction with unsaturated carboxylic acids such as maleic acid, crotonic acid and itaconic acid can also be used. Among them, an acrylic ester or a methacrylic ester monomer can be particularly preferably used.

  The ethylenic compound undergoes addition polymerization together with the photopolymerizable compound of the general formula (1) when the photosensitive resin composition is irradiated with light having a predetermined wavelength. Therefore, the entire composition can be made to have a crosslinked structure.

  Examples of the photopolymerization initiator that can be used in the present invention include 2,2-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (hereinafter, B-CIM (manufactured by Hodogaya Chemical Co., Ltd.)), 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1- Lopan-1-one, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 2-chlorobenzophenone, 4,4′-bisdimethylaminobenzophenone (hereinafter, Michler's ketone), 4,4′-bisdiethylaminobenzophenone (hereinafter referred to as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.)), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- ( 4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Ethyl acetate, butyl 4-dimethylaminobenzoate, 4-di Tylaminobenzoic acid-2-ethylhexyl ester, 4-dimethylaminobenzoic acid-2-isoamyl ester, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, trichloroacetophenone, p-tert -Butylacetophenone, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, bis (4-dimethylamino) Phenyl) ketone, 4,4′-bisdiethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether Ter, benzoin isobutyl ether, benzoin butyl ether, p-dimethylaminoacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2,4-bis (trichloromethyl) -6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methoxy) styryl-s-triazine, etc. And triazine compounds.

  In addition to the above, sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2 -Anthraquinones such as benzanthraquinone and 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercaptobenzoxazole Thiol compounds such as 2-mercaptobenzothiazole can also be used.

  These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type. In particular, B-CIM and EAB-F are preferably used either alone or in combination.

  Specific examples of the combination include B-CIM and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one or 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butan-1-one, B-CIM and 2,4-bis (trichloromethyl) -6- (3-bromo-4-methoxy) phenyl-s-triazine or 2,4 -Bis (trichloromethyl) -6- (p-methoxy) styryl-s-triazine, B-CIM and 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one or 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2,4-bis (trichloromethyl) -6- (3-bromo 4-methoxy) phenyl-s-triazine or 2,4-bis (trichloromethyl) -6- (p-methoxy) styryl-s-triazine in combination, EAB-F and 2-benzyl-2-dimethylamino-1 Combination of-(4-morpholinophenyl) -butan-1-one, combination of triazine, EAB-F, 2-mercaptobenzimidazole and p-methoxystyryltriazine, 2-mercaptobenzimidazole and p-methoxystyryltriazine And the like.

  An insulating organic pigment is used as the black pigment. In the present embodiment, a black-colored perylene-based compound, so-called perylene black, is used. Perylene black is an organic compound that is much less conductive than conductive inorganics such as carbon black.

  In order to improve the blackness of perylene black, a chromatic organic pigment such as a red organic pigment or a blue organic pigment may be added as an auxiliary pigment. The following effects can be obtained by appropriately selecting and adding a chromatic organic pigment having a complementary color of perylene black. For example, with respect to a black pigment exhibiting a reddish black, the redness can be eliminated by adding an organic pigment exhibiting a blue color that is a complementary color of red as an auxiliary pigment, and as a whole, a more preferable black color is exhibited.

  In addition to the red organic pigment and / or the blue organic pigment as an auxiliary pigment to be added to the black pigment, the pigment may further contain an organic pigment exhibiting a color such as yellow or violet. Further, as an auxiliary pigment to be added to the black pigment, an organic pigment exhibiting a color such as yellow or violet may be included without including a red organic pigment and / or a blue organic pigment. The auxiliary pigment is not limited to red, blue, chromatic, yellow, and violet, and an organic pigment exhibiting a necessary color at that time is used according to the blending conditions of the components of the black pigment photosensitive resin composition. Can do.

  Moreover, when forming a black pattern using the photosensitive resin composition of the present invention, as described later, the photosensitive resin composition of the present invention is applied on a substrate and dried to form a photosensitive resin composition layer. Form. In order to improve the coating property and the physical properties after photocuring at this time, a polymer binder may be further contained as a binder in addition to the above components. What is necessary is just to select a binder suitably according to the objectives, such as compatibility, film formation property, developability, and adhesiveness.

  Specific examples of the polymer binder include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate , Isobornyl methacrylate, glycidylme Those obtained by copolymerizing monomers selected from acrylate, styrene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, etc., modified with acidic cellulose having a carboxyl group in the side chain, polyethylene oxide, polyvinylpyrrolidone , Acrylonitrile, vinyl chloride, copolymer of vinylidene chloride, vinylidene chloride, chlorinated polyolefin, or copolymer of vinyl chloride and vinyl acetate, polyvinyl acetate, copolymer of acrylonitrile and styrene, acrylonitrile and styrene, Copolymers with butadiene, polyvinyl alkyl ether, polyvinyl alkyl ketone, polystyrene, polyamide, polyurethane, polyethylene terephthalate isophthalate, acetyl cellulose and poly Or the like can be mentioned butyral. In particular, a monomer having a carboxyl group such as acrylic acid or methacrylic acid is preferably used as a copolymerization component in order to improve developability in an alkaline aqueous solution. The acrylic acid, methacrylic acid and the like are preferably in the range of 5 to 40% by weight in the copolymer component. Moreover, the cellulose resin which made the polybasic acid anhydride react with the hydroxyl group of carboxymethylcellulose, carboxyethylcellulose, carboxypropylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose can also be used preferably.

  The polymer binder can be contained in an amount of 400 parts by weight or less, preferably 200 parts by weight or less, based on 100 parts by weight of the total of the photopolymerizable compound, ethylenic compound, photopolymerization initiator, and black pigment.

  In order to further improve the applicability of the photosensitive resin composition of the present invention, a solvent may be added in addition to the above. Solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2- Methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl Acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methyl Xypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl- 4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol, Examples include hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin. Of these, 3-methoxybutyl acetate can be preferably used.

  The solvent is in a range of 1000 parts by weight or less, preferably 500 parts by weight or less, based on 100 parts by weight of the total of the photopolymerizable compound represented by the general formula (1), the ethylenic compound, the photopolymerization initiator, and the black pigment. Can be contained.

If necessary, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a surfactant, an antifoaming agent, and other additives can be further added to the photosensitive resin composition of the present invention.
Specific examples of the sensitizer include eosin B (C.I.No. 45400), eosin J (C.I.No. 45380), alcohol-soluble eosin (C.I.No. 45386), cyanocin (C I. No. 45410), Bengalrose, erythrosine (C.I. No. 45430), 2,3,7-trihydroxy-9-phenylxanthen-6-one, and xanthene dyes such as rhodamine 6G, thionine ( CI No. 52000), thiazine dyes such as Azure A (CI No. 52005) and Azure C (CI No. 52002), pyronin B (C.I. No. 45005), and Pyronin dyes such as pyronin GY (CI No. 45005), 3-acetylcoumarin, 3-acetyl7-diethylaminocoumarin, etc. They include coumarin compounds.

  As the thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether, p-methoxyphenol, pyrogallol, catechol, 2,6-di-tert-butyl-p-cresol, β-naphthol and the like can be used.

  As the plasticizer, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol and the like can be used.

As the surfactant, various anionic, cationic and nonionic surfactants can be used. As the antifoaming agent, various silicone-based and fluorine-based antifoaming agents can be used.
The black pattern forming method of the present invention includes 1) adjustment of the photosensitive resin composition, 2) formation of the photosensitive resin composition layer on the substrate, 3) exposure, 4) development, and 5) post-baking. Basically it can be formed.
Hereinafter, each process will be described.

1) Preparation of photosensitive resin composition Photosensitive resin composition, 3 roll mill, ball mill with binder, solvent, sensitizer, thermal polymerization inhibitor, plasticizer, surfactant, antifoaming agent, etc. if necessary Disperse and knead well with a sand mill, a jet mill or the like.

2) Formation of photosensitive resin composition layer The photosensitive resin composition prepared above is applied onto a substrate whose surface has been cleaned in advance. Examples of the substrate include materials such as glass, polyethylene terephthalate, and acrylic resin. Moreover, in order to improve the adhesiveness of a board | substrate and the photosensitive resin composition, a silane coupling agent may be added to the photosensitive resin composition, or you may apply | coat to a board | substrate previously. For the application of the photosensitive resin composition, a contact transfer type coating device such as a roll coater, a reverse coater or a bar coater or a non-contact type coating device such as a spinner or a curtain flow coater is used. In particular, in the case of a thick film, it is preferable to apply a plurality of times or to use several kinds of the application devices together. After application of the photosensitive resin composition, it is allowed to stand for several hours to several days at room temperature, or is placed in a warm air heater or infrared heater for several tens of minutes to several hours to remove the solvent, and the coating film thickness is about 1 to 10 μm. The photosensitive resin composition layer.

3) Exposure After formation of the photosensitive resin composition layer, exposure is performed through a negative mask. The light beam having a predetermined wavelength used for exposure is an activation light beam that emits light having a wavelength that activates the photopolymerization initiator to generate radicals, and specifically includes ultraviolet rays, excimer laser light, X-rays, gamma rays, and electron beams. Is preferred. The amount of irradiation light varies slightly depending on the composition of the photosensitive resin composition used, but is preferably in the range of 30 to 2000 mJ / cm ² .

4) Development After the exposure process, development is performed by using a developer by a dipping method, a spray method, or the like. Examples of the developer include alkali metal hydroxides such as lithium, sodium, and potassium, carbonates, bicarbonates, phosphates, pyrophosphates, primary amines such as benzylamine and butylamine, dimethylamine, and dibenzyl. Secondary amines such as amine and diethanolamine, tertiary amines such as trimethylamine, triethylamine and triethanolamine, cyclic amines such as morpholine, piperazine and pyridine, polyamines such as ethylenediamine and hexamethylenediamine, tetraethylammonium hydroxide, trimethylbenzyl Ammonium hydroxide such as ammonium hydroxide, trimethylphenylbenzylammonium hydroxide, trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide, di Sulfonium hydroxides, such as chill benzyl sulfonium hydroxide, an aqueous solution of other choline is used.

5) Post-bake In the post-bake process, the temperature may be adjusted to be in the range of 150 to 250 ° C. in order to impart strength, chemical resistance and heat resistance of the black pattern formed by development.

  As described above, the photosensitive resin composition of the present invention and the black pattern formed using this photosensitive resin composition are particularly suitable as a black matrix for color filters such as liquid crystal displays. As described above, a black pattern that becomes a black matrix pattern is formed on the substrate using the photosensitive resin composition of the present invention, and R, G, B, etc. are colored by a dyeing method, a printing method, a pigment dispersion method, or the like. Since the black matrix portion has a high light shielding property, it is possible to produce a color filter such as a liquid crystal display having a high display contrast, no color leakage and excellent color development.

Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.
[Example 1]
1. Production of photopolymerizable compound A In a 500 ml four-necked flask, 400 g of PGMEA (propylene glycol monomethyl ether acetate), 75 g of methacrylic acid, 210 g of benzyl methacrylate, 15 g of 2-hydroxyethyl methacrylate, 5 g of azobiisobutyronitrile, The photopolymerizable compound A was obtained by stirring and reacting at 65 to 70 degrees for 3 hours while blowing.

2. Preparation of black photosensitive resin composition Photopolymerizable compound (photopolymerizable compound A, DPHA (dipentaerythritol hexaacrylate)), photopolymerization initiator (trade name: CGI369, manufactured by Ciba Specialty Chemicals Co., Ltd.), pigment ( Perylene black, red pigment, blue pigment) were mixed in the following weight ratio. The red pigment is a pigment dispersion “CF Red EX-109” (C.I.P Red-177, containing 20% anthraquinone red pigment), and the blue pigment is a blue pigment dispersion CF Blue UM (C.I. .P blue-15: 6 containing 20%).
Photopolymerizable compound A: DPHA: CGI 369: Perylene black: Red pigment: Blue pigment = 10: 2: 1: 5: 2: 1
To this mixture, MBA (3-methoxybutyl acetate) was added as a solvent, and the mixture was prepared so as to be 20% by weight of MBA to obtain a black photosensitive resin composition.

3. Formation of Black Matrix Pattern Using the spin photosensitive coater (TR25000: manufactured by Tokyo Ohka Kogyo Co., Ltd.) on the glass substrate having a clean surface with a thickness of 1 mm, the black photosensitive resin composition prepared above has a dry film thickness of 2 μm. And dried at 90 degrees for 2 minutes to form a black photosensitive resin composition layer.

  Subsequently, the black photosensitive resin composition layer was selectively irradiated with ultraviolet rays through a negative mask. Thereafter, spray development was performed with a 0.5 wt% sodium carbonate aqueous solution at 25 ° C. for 60 seconds, and then post-baked in an oven at 200 ° C. for 30 minutes to form a black matrix pattern.

[Example 2]
1. Production of photopolymerizable compound A Photopolymerizable compound A was produced in the same manner as in Example 1.

2. Preparation of Black Photosensitive Resin Composition A photopolymerizable compound (photopolymerizable compound A, DPHA), a photopolymerization initiator (CGI369), and a pigment (perylene black, red pigment, blue pigment) were mixed in the following weight ratio. In addition, the red pigment and the blue pigment used the same thing as Example 1.
Photopolymerizable compound A: DPHA: CGI 369: perylene black: red pigment: blue pigment = 10: 2: 1: 1: 0.4: 0.2
To this mixture, MBA (3-methoxybutyl acetate) was added as a solvent, and the mixture was prepared so as to be 20% by weight of MBA to obtain a black photosensitive resin composition.

3. Formation of Black Matrix Pattern A black matrix pattern was formed in the same manner as in Example 1.
[Example 3]
1. Production of photopolymerizable compound A Photopolymerizable compound A was produced in the same manner as in Example 1.

2. Preparation of Black Photosensitive Resin Composition A photopolymerizable compound (photopolymerizable compound A, DPHA), a photopolymerization initiator (CGI369), and a pigment (perylene black, red pigment, blue pigment) were mixed in the following weight ratio. In addition, the red pigment and the blue pigment used the same thing as Example 1.
Photopolymerizable compound A: DPHA: CGI 369: Perylene black: Red pigment: Blue pigment = 10: 2: 1: 25: 10: 5
To this mixture, MBA (3-methoxybutyl acetate) was added as a solvent, and the mixture was prepared so as to be 20% by weight of MBA to obtain a black photosensitive resin composition.
3. Formation of Black Matrix Pattern A black matrix pattern was formed in the same manner as in Example 1.

[Comparative Example 1]
1. Production of photopolymerizable compound A Photopolymerizable compound A was produced in the same manner as in Example 1.

2. Preparation of black photosensitive resin composition A photopolymerizable compound (photopolymerizable compound A, DPHA), a photopolymerization initiator (CGI369), and a black pigment (carbon black) were mixed in the following weight ratio. As the black pigment, carbon dispersion CF black EX-1455 (containing 24% high-resistance carbon: manufactured by Gokoku Dye) was used.
Photopolymerizable compound A: DPHA: CGI 369: black pigment = 10: 2: 1: 8
To this mixture, MBA (3-methoxybutyl acetate) was added as a solvent, and the mixture was prepared so as to be 20% by weight of MBA to obtain a black photosensitive resin composition.
3. Formation of Black Matrix Pattern A black matrix pattern was formed in the same manner as in Example 1.

[Evaluation of Example 1-3 and Comparative Example 1]
The dielectric constant and OD (optical density) of each black matrix pattern formed in Example 1-3 and Comparative Example 1 were measured. Further, the shape of the black matrix pattern was visually evaluated with an optical microscope. The results are shown in Table 1.

表１より実施例１−３で形成したブラックマトリクスパターンの誘電率は比較例１で形成したブラックマトリクスパターンの誘電率よりかなり小さい、すなわち、比較例１より絶縁性の効果が大きいことが確認できる。そして、フォトスペーサーとして利用できるための誘電率は通常７以下であり、実施例１−３で形成したブラックマトリクスパターン誘電率のいずれも７以下であり、フォトスペーサーとして利用することができる。

From Table 1, it can be confirmed that the dielectric constant of the black matrix pattern formed in Example 1-3 is considerably smaller than the dielectric constant of the black matrix pattern formed in Comparative Example 1, that is, the insulating effect is larger than that of Comparative Example 1. . The dielectric constant that can be used as a photospacer is usually 7 or less, and any of the dielectric constants of the black matrix pattern formed in Example 1-3 is 7 or less, and can be used as a photospacer.

Further, from Table 1, the OD of the black matrix pattern formed in Examples 1 and 3 is 1 or more / μm, and it can be confirmed that the black matrix pattern is highly light-shielding.
Further, from Table 1, it can be confirmed that the pattern shape of the black matrix pattern formed in Examples 1 and 2 is also good.

Claims (12)

In the black photosensitive resin composition containing the pigment component including the black pigment,
The black pigment resin composition, wherein the pigment component comprises an insulating organic pigment. The black photosensitive resin composition according to claim 1, wherein the black pigment is perylene black. The black photosensitive resin composition according to claim 1, wherein the pigment component includes a red organic pigment and a blue organic pigment. The dielectric constant of the film formed with the said black photosensitive resin composition is 7 or less. The black photosensitive resin composition of any one of Claims 1-3 characterized by the above-mentioned. 5. The black photosensitive resin composition according to claim 1, wherein an optical density of the film formed of the black photosensitive resin composition is 1 or more per 1 μm of film thickness. .   The black photosensitive resin composition according to claim 1, wherein the black photosensitive resin composition includes a photopolymerizable compound, a photopolymerization initiator, and a solvent. The pigment component is contained in a proportion of 20% by weight to 250% by weight with respect to the total weight of the photopolymerizable compound, the photopolymerization initiator, and the solvent. The black photosensitive resin composition of any one of Claims.   A black matrix formed from the black photosensitive resin composition according to claim 1.   An organic electroluminescence display panel comprising the black matrix according to claim 8.   A liquid crystal display panel comprising the black matrix according to claim 9.   The photo spacer formed from the black photosensitive resin composition of any one of Claims 1-7.   A liquid crystal display panel comprising the photospacer according to claim 11.