JP2010282049A - Green photosensitive coloring composition and color filter using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a green photosensitive coloring composition wherein electric characteristics of a coloring layer does not give adverse influence on alignment of a liquid crystal and display performance free from alignment disturbance of the liquid crystal on the periphery of an ITO aperture part can be secured even if an over coat layer is not provided on a color filter in the color filter used for an ITO etching system liquid crystal display device and to provide the color filter. <P>SOLUTION: In the green photosensitive coloring composition containing at least (a) a transparent resin, (b) a multifunctional monomer having three or more ethylenically unsaturated double bonds, (c) a photopolymerization initiator, (d) a coloring material comprising a green pigment and a yellow pigment and (e) a solvent, the transparent resin (a) has 50 to 130 mg/g acid value and a coating film formed by curing the green photosensitive coloring composition has ≥1.0×10<SP>14</SP>Ωcm volume resistivity. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a green photosensitive coloring composition and a color filter for a liquid crystal display device using the same, and more particularly to a vertical alignment (MVA) type liquid crystal display device in which an opening is formed in a transparent conductive film as an electrode. The present invention relates to a suitable green photosensitive coloring composition for a color filter, and a color filter.

  Color liquid crystal display devices are rapidly spreading mainly in computer terminal display devices and television image display devices. The color filter is an indispensable important component for color display of a liquid crystal display device. In recent years, this liquid crystal display device has a strong demand for higher image quality, and a new technology for realizing a high viewing angle and high-speed response to meet this demand has appeared.

  Among these, for example, as disclosed in Patent Document 1, an opening is formed by etching or the like in a transparent conductive film (indium-tin-oxide: hereinafter referred to as ITO) provided on the colored pixels of the color filter, A PVA method (Patterned Vertical Alignment, hereinafter referred to as an ITO etching method in the present specification) that controls the direction in which the liquid crystal is tilted by using electric lines of force from the side surface of the opening toward the electrode of the opposing substrate, This method is easier to manufacture than the MVA (Multiple Vertical Alignment) method, which uses the slope of the resist projections, and is widely used because of its excellent display quality such as viewing angle, brightness, contrast ratio, and response speed. It is.

  However, while the ITO etching method has excellent characteristics in display quality, the colored pixels are changed to electric lines of force (strong electric field) that curve from the side of the ITO opening side to the opposite direction once in the lateral direction. There is a problem that it is exposed and directly affected. When the coloring layer material is easily affected by strong electric lines of force, whether or not the distribution of electric lines of force is significantly different from the case where it is difficult to receive depends on the dielectric properties of the colored layer. In fact, it has been found that when a conventional color filter is used, display defects such as liquid crystal alignment disturbance occur around the opening, and the alignment disturbance particularly in the green pixel portion is remarkable.

  The dielectric properties of this colored layer are mainly due to the properties of the pigment that composes the colored layer, and it is difficult to fundamentally change the pigment itself. When used in an apparatus, a protective layer (overcoat layer) made of a transparent resin is provided on the colored layer, and a layer configuration has been adopted in which the lines of electric force do not penetrate into the colored layer below as much as possible.

  On the other hand, in color filters used in existing vertical liquid crystal display devices and IPS (lateral electric field) type liquid crystal display devices, for example, patent documents 2 and 3 disclose the overcoat layer which is expensive. Thus, attempts have been made to increase the insulation of the colored pixel layer of the color filter. However, in an ITO etching type color filter for a liquid crystal display device, the requirement for insulation is not sufficient to the extent required by an existing liquid crystal display device.

  In recent years, the price of liquid crystal display devices has been remarkably reduced, and the color filter that is a member of the liquid crystal display device is also required to be reduced in price. As described above, by providing an overcoat layer of transparent resin, it is possible to use a conventional color filter in an ITO etching type liquid crystal display device, but the cost increases due to increased material costs and processes. Therefore, a color filter that can be used in an ITO etching type liquid crystal display device without providing an overcoat layer has been desired.

JP 2002-6132 A JP 2003-139936 A JP 2002-122858 A

  The present invention relates to a color filter used in an ITO etching type liquid crystal display device, in which the electrical characteristics of the colored layer do not adversely affect the alignment of the liquid crystal, and the ITO opening can be formed without providing an overcoat layer on the color filter. It is an object of the present invention to provide a green photosensitive coloring composition capable of ensuring display performance without disturbing the alignment of liquid crystal around the portion and a color filter using the same.

The invention according to claim 1 of the present invention relates to a green photosensitive coloring composition used for a color filter for a liquid crystal display device having a configuration in which a colored pixel is in contact with a liquid crystal through an opening provided in a transparent conductive film. The photosensitive coloring composition contains at least (a) a transparent resin, (b) a polyfunctional monomer having three or more ethylenically unsaturated double bonds, (c) a photopolymerization initiator, (d) a green pigment, and yellow A colorant comprising a pigment, and (e) a volume of a coating film containing the solvent, wherein the transparent resin (a) has an acid value of 50 to 130 mg / g, and the green photosensitive coloring composition is hardened A green photosensitive coloring composition having a resistivity of 1.0 × 10 ¹⁴ Ω · cm or more.
Here, the acid value is an acidic group content determined by an acid value reduction titration method using an aqueous potassium hydroxide (KOH) solution.

（式（１）において、中心金属は銅であり、外周の４個のベンゼン環に結合した１６個のＸのうち、１４．５〜１５．６平均して１５個は臭素原子である。） Further, the invention according to claim 2 of the present invention is that the green pigment is a chlorinated brominated copper phthalocyanine pigment having an average of 15 bromine atoms per molecule represented by the chemical formula (1). It is the green photosensitive coloring composition of Claim 1 characterized by the above-mentioned.

(In the formula (1), the central metal is copper, and among the 16 X bonded to the four benzene rings on the outer periphery, 14.5 to 15.6 average 15 are bromine atoms.)

（式（２）において、Ｒ_１は、水素原子またはメチル基を表し、Ｒ_２は、炭素数２〜１０のアルキレン基を表し、Ｒ_３は、水素原子又はベンゼン環を含むこともある炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。） The invention according to claim 3 of the present invention is characterized in that the transparent resin (a) contains an ethylenically unsaturated monomer represented by the following chemical formula (2) as a copolymerization component. The green photosensitive coloring composition described in 1.

(In Formula (2), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a carbon atom that may contain a hydrogen atom or a benzene ring. Represents an alkyl group of 1 to 20. n represents an integer of 1 to 15.)

  Next, an invention according to claim 4 of the present invention is a color filter comprising a pixel electrode having at least a black matrix and a plurality of colored pixels on a transparent substrate, and having a slit provided on each pixel. It is a color filter manufactured using the green photosensitive coloring composition as described in any one of Claim 1 to 3 to a green pixel.

In the present invention, in the green photosensitive coloring composition that is easily affected by the lines of electric force and easily affects the alignment of the liquid crystal, the volume resistivity is set by setting the acid value of the transparent resin within the optimum range. Of 1.0 × 10 ¹⁴ Ω · cm or more. Therefore, even if it is used for the green pixel of an ITO etching type liquid crystal display device, the green pixel is less affected by the electric lines of force, and the disturbance of the electric lines of force is reduced, so that an overcoat layer is formed on the color filter. Even if it is not provided, it is possible to provide a color filter that does not disturb the alignment of the liquid crystal due to the disturbance of the lines of electric force around the ITO opening, that is, does not adversely affect the display performance.

  Hereinafter, the present invention will be first summarized, and then the details of the material surface, the general production method of the photosensitive coloring composition, and the production method of the color filter substrate will be described in detail.

  The green photosensitive coloring composition according to the present invention includes, as its essential components, (a) a transparent resin, (b) a polyfunctional monomer having three or more ethylenically unsaturated double bonds, and (c) a photopolymerization initiator. , (D) a coloring material, and (e) a solvent. Moreover, you may contain additives, such as a dispersing agent, a photosensitizer, and a chain transfer agent.

And the acid value of the transparent resin (a) in the green photosensitive coloring composition is in the range of 50 to 130 mg / g, and the coating film of the green photosensitive coloring composition is hardened to form a colored pixel layer. The volume resistivity is 1.0 × 10 ¹⁴ Ω · cm or more.

  When the acid value of the transparent resin (a) is higher than 130 mg / g, the dielectric property improving effect is insufficient and the volume resistivity does not increase. Moreover, when the acid value of transparent resin (a) is less than 50 mg / g, the solubility with respect to the alkaline developing solution of the coating film of a green photosensitive coloring composition becomes low, and patterning property worsens.

  Next, each component which comprises the green photosensitive coloring composition of this invention is demonstrated.

[(A) Transparent resin]
The transparent resin that can be used in the green photosensitive coloring composition of the present invention is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a non-photosensitive resin such as a thermoplastic resin and a thermosetting resin, and a photosensitive resin. Furthermore, if necessary, a monomer or an oligomer that is a precursor thereof and is cured by irradiation with radiation to form a transparent resin can be used alone or in combination of two or more.

  The non-photosensitive resin is a resin having no ethylenically unsaturated double bond. Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, and polyvinyl chloride. , Vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polybutadiene, etc. Can be mentioned. Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a phenol resin, a melamine resin, a urea resin, and a polyimide resin. However, most of these resins do not show alkali solubility.

At present, as the developer, an alkaline developer having a small influence on the environment is often used. For this reason, it is desirable to use an alkali-soluble resin as the resin binder. The alkali-soluble non-photosensitive transparent resin is a transparent resin having a property of dissolving in an alkaline aqueous solution and having no ethylenically unsaturated double bond. For example, an acidic functional group such as a carboxyl group or a sulfone group Non-photosensitive transparent resin having a mass average molecular weight of 1,000 to 500,000, preferably 5,000 to 10,000. Of the acidic functional groups, a carboxyl group is preferred. In order to stabilize dispersion and improve the development performance of the color filter coloring composition, the acid value of the non-photosensitive transparent resin is preferably higher than the acid value of the photosensitive transparent resin. The patterning property of the transparent colored coating film made of the composition is improved, and a transparent colored pixel having a stable shape is obtained.

  Specific examples of such alkali-soluble non-photosensitive resins include acrylic resins having acidic functional groups, α-olefin- (anhydrous) maleic acid copolymers, styrene- (anhydrous) maleic acid copolymers, and styrene. -Styrenesulfonic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene- (anhydrous) maleic acid copolymer and the like. Among them, at least one kind selected from an acrylic resin having an acidic functional group, an α-olefin- (anhydrous) maleic acid copolymer, a styrene- (anhydride) maleic acid copolymer, and a styrene-styrene sulfonic acid copolymer. Resins are preferably used. Among these, acrylic resins having acidic functional groups are preferably used because of their high heat resistance and transparency. A resin having a mass average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000 can be preferably used.

  As the photosensitive resin, a linear polymer having a reactive functional group is reacted with a (meth) acrylic compound having a substituent capable of reacting with the reactive functional group, cinnamic acid, or the like to react with an ethylenically unsaturated double polymer. Examples thereof include resins in which a bond is introduced into the linear polymer. In addition, a linear polymer having a substituent capable of reacting with the reactive functional group is reacted with a (meth) acrylic compound having a reactive functional group, cinnamic acid, or the like, to thereby form an ethylenically unsaturated double bond. Resin introduced into the polymer. Examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group, and examples of the substituent capable of reacting with the reactive functional group include an isocyanate group, an aldehyde group, and an epoxy group.

  In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Those half-esterified with can be used as the photosensitive resin.

  The amount of ethylenically unsaturated double bonds introduced through a hydroxyl group or the like into the photosensitive transparent resin, which indicates the ease of photocuring, is indicated by the “double bond equivalent” of the resulting photosensitive transparent resin. . The double bond equivalent of the photosensitive transparent resin in the present invention is preferably 200 to 1200, and more preferably 300 to 900. When the double bond equivalent of the photosensitive transparent resin is less than 200, the ratio of the ethylenically unsaturated monomer having a reactive substituent for introducing an ethylenically unsaturated double bond is increased, and various characteristics are maintained. A sufficient amount of other ethylenically unsaturated monomers cannot be copolymerized. When it exceeds 1200, sufficient sensitivity cannot be obtained because the number of ethylenically unsaturated double bonds is small. Moreover, the mass average molecular weight (Mw) of the photosensitive transparent resin is preferably 2000 to 200000, more preferably 5000 to 50000, from the viewpoint that the dispersibility of the red colorant is good.

(Other components in transparent resin)
When a pigment is used as the colorant, it is preferable from the viewpoint of improving the dispersion stability of the pigment that the transparent resin contains an ethylenically unsaturated monomer (A) represented by the following chemical formula (2) as a polymerization component.

In Formula (2), R ₁ represents a hydrogen atom or a methyl group, and R ₂ has 2 to 10 carbon atoms.
R ₃ represents an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring. n represents an integer of 1 to 15.

The alkylene group of R ₂ has 2 to 10 carbon atoms, and more preferably has 2 to 3 carbon atoms. Although the carbon number of the alkyl group of _{R 3} is 1 to 20, more preferably 1 to 10, alkyl group of _{R 3} may include a benzene ring. When the carbon number of the alkyl group of R ₃ is 1 to 10, the alkyl group becomes an obstacle and suppresses the approach between the resins and promotes adsorption / orientation to the pigment, but when the carbon number exceeds 10, the alkyl group The steric hindrance effect increases, and the adsorption / orientation of the benzene ring to the pigment tends to be hindered. This tendency becomes more prominent as the carbon chain length of the alkyl group of R ₃ becomes longer. When the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely reduced. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

  Examples of the ethylenically unsaturated monomer (A) include phenol ethylene oxide (EO) -modified (meth) acrylate, paracumylphenol EO or propylene oxide (PO) -modified (meth) acrylate, and nonylphenol EO-modified (meth). Examples thereof include acrylate, PO-modified (meth) acrylate of nonylphenol and the like. Among these compounds, EO or PO-modified (meth) acrylate of paracumylphenol is better for coloring materials such as pigments, in addition to the effect of π electrons on the benzene ring as well as its steric effect. Since a simple adsorption / orientation plane can be formed, the dispersion effect is higher.

  In order to use the ethylenically unsaturated monomer (A) as a photosensitive transparent resin or a non-photosensitive transparent resin, it is necessary to copolymerize with another ethylenically unsaturated monomer (B). is there. Other ethylenically unsaturated monomers (B) copolymerizable with the ethylenically unsaturated monomer (A) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (iso ) Propyl (meth) acrylate, (iso) butyl (meth) acrylate, (iso) pentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (Meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate, acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, 3-chloro-2-acid phosphooxyethyl (meth) acrylate, Acid Phospho Shi polyethylene glycol mono (meth) acrylate and the like, these can be used alone or in combination.

  An ethylenically unsaturated monomer (A) in a photosensitive or non-photosensitive transparent resin obtained by copolymerizing an ethylenically unsaturated monomer (A) and another ethylenically unsaturated monomer (B). The copolymerization ratio of (A) and (B) is preferably 0.1 to 50% by mass, more preferably 10 to 35% by mass, based on the total mass of the monomers combined with (A) and (B). When the copolymerization ratio of the ethylenically unsaturated monomer (A) is less than 0.1% by mass, the pigment dispersion effect is lowered. On the other hand, when the amount is more than 50% by mass, the hydrophobicity is increased, and the developability of the coloring composition may be lowered or a residue may be caused.

[(B) Multifunctional monomer]
The photopolymerizable monomer as the polyfunctional monomer is polymerized by irradiation with exposure light, and changes the colored photosensitive layer produced using the photosensitive coloring composition to be insoluble in the developer. Generally, it is a monomer whose polymerization is induced by radicals.

  As such a photopolymerizable monomer, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate can be used.

  As the (meth) acrylate having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (Meth) acrylate, dipentaerythritol caprocalactone modified penta (meth) acrylate, glycerol acrylate methacrylate Over DOO, glycerol dimethacrylate, 2-hydroxy-3-acryloyl propyl methacrylate, epoxy group-containing compound and the carboxy (meth) reaction product of acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

  In consideration of the temporal stability and developability of the green photosensitive coloring composition of the present invention and the tackiness of the formed colored layer, the content of the photopolymerizable monomer is 20 mass of the green photosensitive coloring composition. % Or less is preferable. Moreover, it is preferable that it is 1 mass% or more from a viewpoint of exposure sensitivity, the resolution of a pattern, and solvent resistance.

[(C) Photopolymerization initiator]
As the photopolymerization initiator according to the present invention, an oxime ester polymerization initiator can be preferably used. For example, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 '-Methoxy-naphthyl) ethylidene) hydroxylamine, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime).

  In addition to the oxime ester polymerization initiator, other polymerization initiators can be used in combination. Examples of such polymerization initiators include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, phosphine compounds, quinone compounds, borate compounds, carbazole compounds, and imidazole compounds. And titanocene compounds. Examples of acetophenone compounds include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and 1-hydroxy. Cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Examples include 1-one. Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal. Examples of the benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and the like. Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and the like. Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (p-methoxyphenyl) -4,6-bis. (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2 , 4-Bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1) -Yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-me Kishisuchiriru) -6-triazine and the like. Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Examples of the quinone compound include 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone.

  In the green photosensitive coloring composition of the present invention, the use amount of the photopolymerization initiator is preferably 0.5 to 50% by mass, more preferably 3 to 30 based on the total solid content of the photosensitive coloring composition. % By mass.

(Photosensitizer)
In addition to the polymerization initiator, it is preferable to add a photosensitizer to the green photosensitive coloring composition of the present invention. An example of the photosensitizer is an amine compound. For example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-dimethylaminobenzoate 2-ethylhexyl acid, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, etc. is there.

  Α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone or the like can also be used as a photosensitizer.

  The use amount of these photosensitizers is preferably 0.5 to 60% by mass, more preferably 3 to 40% by mass based on the total amount of the photopolymerization initiator and the photosensitizer.

  The green photosensitive coloring composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine.

  The amount of the polyfunctional thiol used is preferably 0.1 to 30% by mass based on the total solid content of the colored composition. If the amount is less than 0.1% by mass, the effect of adding the polyfunctional thiol is insufficient. If the amount exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

[(D) Colorant]
The specific example of the organic pigment which can be used for the green photosensitive coloring composition of this invention is shown with a color index number.

  Examples of the green photosensitive coloring composition for forming a green pixel include C.I. I. Pigment Green 7, 10, 36, 37, 58 or the like can be used in combination. A yellow pigment can be used in combination with the green photosensitive coloring composition. In the present invention, the main green pigment is a halogenated metal phthalocyanine pigment, and the halogenated copper phthalocyanine pigment is representative as a green color filter pigment, and has excellent spectral transmission spectral characteristics and weather resistance. Most preferably used in the present invention is a chlorinated brominated copper phthalocyanine pigment containing an average of 15 bromine atoms in one molecule, and the measured value of the content of bromine as an aggregate of pigments is 14.5 to 15 .6 is used. In order to increase the volume resistivity of the green coating film obtained by hardening the green photosensitive coloring composition, it is desirable that the bromination number is greater than 14.5, and if the bromination number exceeds 15.6, the yellow color becomes yellowish. Is not preferable because it becomes stronger.

  Examples of yellow pigments include C.I. I. In addition to Pigment Yellow 150, 138, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 139, 144, 146, 147, 148, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 1 75, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 and the like.

(Dispersant)
When a pigment is used as the colorant, a dispersant such as a resin-type pigment dispersant, a dye derivative, or a surfactant can be appropriately used. Since the dispersant is excellent in pigment dispersion and has a great effect of preventing reaggregation of the pigment after dispersion, a red coloring composition obtained by dispersing the pigment in the photosensitive resin composition using the dispersant was used. In this case, a color filter having excellent transparency can be obtained. The addition amount of the dispersant is not particularly limited, but is preferably 0.1 to 40% by mass, more preferably 0.1 to 30% by mass, and still more preferably 1 to 100% by mass with respect to 100% by mass of the colorant. It can be used in an amount of 10% by weight.

(Resin type pigment dispersant)
The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the photosensitive transparent resin and the non-photosensitive transparent resin. It functions to stabilize dispersion in the resin composition. Resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polycarboxylic acid esters Siloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are also used. These can be used alone or in admixture of two or more.

  Commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen SOLSPERS E-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32 manufactured by Abyssia 00, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402 manufactured by Efka Chemicals , 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used singly or in combination of two or more.

(Surfactant)
Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as laurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline These can be used alone or in admixture of two or more.

(Storage stabilizer)
The green photosensitive coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

(solvent)
In order to make it easy to form a filter segment by coating the green photosensitive coloring composition of the present invention on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to optimize the viscosity of the photosensitive coloring composition and sufficiently disperse the coloring agent uniformly in the photosensitive resin composition, a solvent can be contained. As the solvent, water, an organic solvent, or the like can be used. Examples of the organic solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone. , Propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination. The solvent can be used in an amount of preferably 800 to 4000 parts by mass, more preferably 1000 to 2500 parts by mass with respect to 100 parts by mass of the colorant.

Next, the preparation method of the photosensitive coloring composition of this invention is demonstrated. The green photosensitive coloring composition of the present invention can be prepared, for example, from a photopolymerizable monomer, a transparent resin, a pigment, a dispersant, and a solvent by any one of the following methods (1) to (4).
(1): A pigment composition prepared by mixing a pigment and a dispersant in advance is added to a solution obtained by dissolving a photopolymerizable monomer and / or transparent resin in a solvent, and dispersed, and the remaining components are added. .
(2): A pigment and a dispersant are separately added and dispersed in a solution in which a photopolymerizable monomer and / or transparent resin or both are dissolved in a solvent, and then the remaining components are added.
(3): A pigment is dispersed in a solution obtained by dissolving a photopolymerizable monomer or a transparent resin or both in a solvent, a pigment dispersant is added, and then the remaining components are added.
(4): Prepare two types of solutions in which a photopolymerizable monomer or transparent resin or both are dissolved in a solvent, disperse the pigment and the dispersant separately in advance, then mix them and add the remaining components To do. One of the pigment and the dispersant may be dispersed only in the solvent.

  Here, the pigment and the dispersant can be dispersed using various dispersing devices such as a three-roll mill, a two-roll mill, a sand mill, a kneader, a dissolver, a high speed mixer, a homomixer, an attritor, and a paint conditioner.

  Moreover, when preparing a pigment composition by mixing a pigment and a dispersant in advance, it is possible to simply mix a powdered pigment and a powdered dispersant, but (b) a kneader, a roll, an attritor, a super mill, etc. Mix mechanically with various pulverizers, or (b) Disperse the pigment in the solvent, then add a solution containing the dispersant to adsorb the dispersant on the pigment surface, or (c) Strongly dissolve sulfuric acid, etc. It is preferable to employ a mixing method in which the pigment and the dispersant are co-dissolved in a powerful solvent and then co-precipitated using a poor solvent such as water.

  Hereinafter, a method for obtaining the color filter of the present invention will be described. The color filter of the present invention includes a plurality of color pixels on at least a transparent substrate, and the plurality of color pixels includes at least a colored layer. Multiple colors include combinations of red, green, and blue (additive color mixing type) and yellow, magenta, and cyan (subtractive color mixing type). The color filter of the present invention is different from a color filter having a green coloring layer. It can be applied particularly preferably.

The transparent substrate used in the color filter of the present invention preferably has a certain degree of transmittance with respect to visible light, and more preferably has a transmittance of 80% or more. Generally, it may be one used in a liquid crystal display device, and examples thereof include a plastic substrate such as PET and glass, but a glass substrate is usually used. In the case of using a light shielding pattern, it is only necessary to use a metal thin film such as chrome or a pattern made of a light shielding resin previously attached to the transparent substrate by a known method.

  The colored layer is formed on the transparent substrate by a photolithography method as described below. That is, a photosensitive coloring composition in which a pigment is dispersed in an appropriate solvent together with a photoinitiator and a polymerizable monomer in a transparent resin is applied to a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. To apply a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a predetermined pattern mask provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion and forming a desired pattern, the polymerization of the colored resist material is promoted as necessary. Heating can also be applied. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, a film that prevents polymerization inhibition by oxygen by applying and drying a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin after coating and drying the photosensitive coloring composition. Ultraviolet exposure can also be performed after forming.

  A color filter having a plurality of color pixels can be obtained by repeating the above-described series of steps by changing the photosensitive coloring composition and pattern as many times as necessary.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited thereto without departing from the spirit of the present invention. In the following examples, parts are parts by mass.

[Resin adjustment]
(Synthesis example of transparent resin 1)
370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 8 parts of methacrylic acid, 13.8 parts of 2-hydroxyethyl methacrylate, 26.3 parts of benzyl methacrylate, n -26.1 parts of butyl methacrylate, 26.3 parts of paracumylphenol ethylene oxide modified acrylate ("Axix M110" manufactured by Toagosei Co., Ltd.) as the ethylenically unsaturated monomer (A), 2,2'-azobis A mixture of 0.4 parts of isobutyronitrile was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by mass. A resin solution was prepared by addition. The obtained transparent resin 1 had a mass average molecular weight Mw of 12000 and a resin acid value of 50 mg / g.

(Synthesis example of transparent resin 2)
370 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 13 parts of methacrylic acid, 14 parts of 2-hydroxyethyl methacrylate, 25 parts of benzyl methacrylate and n-butyl methacrylate 23 at the same temperature. Parts, 25 parts of paracumylphenol ethylene oxide-modified acrylate (“Axix M110” manufactured by Toagosei Co., Ltd.) as ethylenically unsaturated monomer (A), 0.4 part of 2,2′-azobisisobutyronitrile The mixture was added dropwise over 2 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by mass. A resin solution was prepared by addition. The obtained transparent resin 2 had a mass average molecular weight Mw of 12000 and a resin acid value of 80 mg / g.

(Synthesis example of transparent resin 3)
370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 17.5 parts of methacrylic acid, 14.2 parts of 2-hydroxyethyl methacrylate, 24 parts of benzyl methacrylate, n -21 parts of butyl methacrylate, 24 parts of paracumylphenol ethylene oxide-modified acrylate ("Acnics M110" manufactured by Toa Gosei Co., Ltd.) as the ethylenically unsaturated monomer (A), 2,2'-azobisisobutyronitrile 0.4 part of the mixture was added dropwise over 2 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by mass. A resin solution was prepared by addition. The obtained transparent resin 3 had a mass average molecular weight Mw of 12000 and a resin acid value of 105 mg / g.

(Synthesis example of transparent resin 4)
370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 19 parts of methacrylic acid, 14.2 parts of 2-hydroxyethyl methacrylate, 23.5 parts of benzyl methacrylate, n -20 parts of butyl methacrylate, 23.5 parts of paracumylphenol ethylene oxide modified acrylate ("Axix M110" manufactured by Toa Gosei Co., Ltd.) as the ethylenically unsaturated monomer (A), 2,2'-azobisisobuty A mixture of 0.4 part of nitrile was added dropwise over 2 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by mass. A resin solution was prepared by addition. The obtained transparent resin 4 had a mass average molecular weight Mw of 12000 and a resin acid value of 130 mg / g.

(Synthesis example of transparent resin 5)
Put 370 parts of cyclohexanone in a reaction vessel, heat to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 7 parts of methacrylic acid, 14 parts of 2-hydroxyethyl methacrylate, 26.5 parts of benzyl methacrylate, n-butyl 26.5 parts of methacrylate, 26.5 parts of paracumylphenol ethylene oxide-modified acrylate (“Acnics M110” manufactured by Toagosei Co., Ltd.) as the ethylenically unsaturated monomer (A), 2,2′-azobisisobuty A mixture of 0.4 part of nitrile was added dropwise over 2 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by mass. A resin solution was prepared by addition. The obtained transparent resin 5 had a mass average molecular weight Mw of 12000 and a resin acid value of 40 mg / g.

(Synthesis example of transparent resin 6)
Put 370 parts of cyclohexanone in a reaction vessel, heat to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 22 parts of methacrylic acid, 14.5 parts of 2-hydroxyethyl methacrylate, 23 parts of benzyl methacrylate, n-butyl 18 parts of methacrylate, 23 parts of paracumylphenol ethylene oxide modified acrylate (“Axix M110” manufactured by Toa Gosei Co., Ltd.) as the ethylenically unsaturated monomer (A), 2,2′-azobisisobutyronitrile 4 parts of the mixture was added dropwise over 2 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by mass. A resin solution was prepared by addition. The obtained transparent resin 6 had a mass average molecular weight Mw of 12000 and a resin acid value of 140 mg / g.

(Synthesis example of transparent resin 7)
570 parts of cyclohexanone is placed in a reaction vessel and heated to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 23.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 35.0 parts of benzyl methacrylate, ethylenic 22.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) as unsaturated monomer (A), 48.0 parts of glycerol monomethacrylate, 2,2′-azobisisobutyro A mixture of 3.0 parts of nitrile was added dropwise over 1 hour to conduct a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. Next, a mixture of 33.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate, and 130.0 parts of cyclohexanone was added at 3O <0> C to 336 parts of the obtained transparent resin copolymer solution. The solution was dropped over time to obtain a transparent resin solution. After cooling to room temperature, about 2 g of the transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by mass. A resin solution was prepared by addition. The obtained transparent resin 7 had a mass average molecular weight Mw of 21,000 and a resin acid value of 50 mg / g.

(Synthesis example of transparent resin 8)
370 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 12.3 parts of benzyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 5.3 parts of methacrylic acid at the same temperature. , 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.) as ethylenically unsaturated monomer (A), 0.4 part of 2,2′-azobisisobutyronitrile The mixture was added dropwise over 2 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by mass. A resin solution was prepared by addition. The obtained transparent resin 8 had a mass average molecular weight Mw of 20000 and a resin acid value of 80 mg / g.

[Preparation of photosensitive coloring composition]
Red, blue and green photosensitive coloring compositions were prepared as follows.

(Red photosensitive coloring composition)
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a red pigment dispersion.
-Red pigment: C.I. I. Pigment Red 254
(“Ilgar For Red B-CF” manufactured by Ciba Specialty Chemicals) 9 parts Red pigment: C.I. I. Pigment Red 177
("Chromophthal Red A2B" manufactured by Ciba Specialty Chemicals) 1 part Dispersant ("Ajisper PB821" manufactured by Ajinomoto Fine Techno Co.) 2 parts Transparent resin 8 (solid content 20%) 40 parts Propylene glycol monomethyl 48 parts of ether acetate

Thereafter, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 5 μm filter to obtain a red photosensitive coloring composition.
・ Dispersion of the above red pigment 57 parts ・ Transparent resin 8 (solid content 20%) 18.3 parts ・ Polyfunctional monomer (DPPAH: dipentaerythritol pentaacrylate hexamethylene diisocyanate) 2.8 parts ・ Photoinitiator (Ciba "Irgacure 907" manufactured by Japan Co., Ltd.) 0.8 parts-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.3 parts-20.7 parts cyclohexanone

(Blue photosensitive coloring composition)
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a blue pigment dispersion.
Blue pigment: C.I. I. Pigment Blue 15
(Toyo Ink Manufacturing Co., Ltd. “Lionol Blue ES”) 9 parts Purple pigment: C.I. I. Pigment Violet 23
(BASF "Paliogen Violet 5890") 1 part Dispersant (Zeneca "Sols Birds 20000") 2 parts Transparent resin 8 (solid content 20%) 40 parts Propylene glycol monomethyl ether acetate 48 parts

Thereafter, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 5 μm filter to obtain a blue photosensitive coloring composition.
-57 parts of the above blue pigment dispersion-13.1 parts of transparent resin 7 (solid content 20%)-polyfunctional monomer (DPPAH: dipentaerythritol pentaacrylate hexamethylene diisocyanate) 3.3 parts-photoinitiator (Ciba "Irgacure 907" manufactured by Japan Co., Ltd.) 1.2 parts. Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts. 25 parts of propylene glycol monomethyl ether acetate.

(Green photosensitive coloring composition 1)
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a green pigment dispersion.
Green pigment: C.I. I. Pigment Green 36
(Toyo Ink Mfg. Co., Ltd. “Lionol Green 6Y501”) 14 parts Dispersant (Big Chemie “Disperbyk-163”) 2 parts Transparent resin 8 (solid content 20%) 20 parts Propylene glycol monomethyl ether acetate 64 copies

Next, a mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a yellow pigment dispersion.
-Yellow pigment: C.I. I. Pigment Yellow 150
("Funchon First Yellow Y-5688" manufactured by Bayer) 10 parts Dispersant ("Disperbyk-163" manufactured by Big Chemie) 2 parts Transparent resin 8 (solid content 20%) 40 parts Propylene glycol monomethyl ether acetate 48 Part

Thereafter, using the green pigment dispersion and the yellow pigment dispersion, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 5 μm filter to obtain a green photosensitive coloring composition 1. It was.
Green pigment dispersion 1 35.8 parts Yellow pigment dispersion 12.5 parts Transparent resin 1 (solid content 20%) 30.3 parts Polyfunctional monomer (DPPAH: dipentaerythritol pentaacrylate hexamethylene diisocyanate) 2 .8 parts-Photoinitiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.) 0.3 parts-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts-Propylene glycol Monomethyl ether acetate 18.1 parts

(Green photosensitive coloring composition 2-6)
Instead of the transparent resin 1 used in the above-described green photosensitive coloring composition 1, the green photosensitive coloring compositions 2, 3, 4, 5, and 6 are transparent resins 2, 3, 4, 5, and 6, respectively. It was obtained by adding the same composition ratio.

  As the photosensitive coloring composition for producing the green filter segments (pixels), the color filters produced using the green photosensitive coloring compositions 1 to 4 are referred to as Examples 1 to 4, and the green photosensitive coloring compositions 5 and 6 are used. The color filters produced using these were designated as Comparative Examples 1 and 2. Moreover, a red photosensitive coloring composition is used for the photosensitive coloring composition for producing the red filter segment (pixel), and a blue photosensitive coloring composition is used for the photosensitive coloring composition for producing the blue filter segment (pixel). It was.

[Evaluation item]
(Volume resistivity)
The green photosensitive coloring composition was applied to a glass substrate having a thickness of 3.5 μm using a spin coater on a 100 mm × 100 mm, 0.7 mm thick glass substrate on which aluminum was deposited for an electrode to obtain a coated substrate. Next, after drying under reduced pressure, ultraviolet exposure was performed using an ultrahigh pressure mercury lamp with an integrated light amount of 100 mJ and an illuminance of 30 mW. After alkali development, the coated substrate is heated at 230 ° C. for 40 minutes and allowed to cool. On the resulting cured coating film, aluminum for an electrode having an area of 1 cm ² is deposited, and a sample in which the green coating film is sandwiched between aluminum electrodes is prepared. Produced. The volume resistivity of the obtained sample was measured with a minute current measuring instrument (“Type 237” manufactured by Keithley).
(Poor orientation)
A liquid crystal display device using an ITO etching method was prepared, and liquid crystal alignment failure was confirmed.
(Developability)
Solubility in alkaline developer. After the exposure, development was performed for 2 minutes. A pattern was formed with no resist residue, and a pattern was not formed.

The results of Examples 1 to 3 are shown in Table 1, and the results of Comparative Examples 1 and 2 are shown in Table 2.
The marks shown in Tables 1 and 2, for example, 10E + 15, mean 10 to the 15th power.

<Comparison result>
From the results in Table 1, the following is clear. That is, in the green photosensitive coloring composition, when the acid value of the transparent resin (a) is 50 to 130 mg / g, the volume resistivity becomes 1.0 × 10 ¹⁴ Ω · cm or more, resulting in poor alignment. There was no. Furthermore, there was obtained a color filter in which there was no resist residue and a pattern was formed. On the other hand, from the results in Table 2, when the resin acid value was 40 or less, no pattern was formed. Further, as the acid value of the resin increased, the volume resistivity decreased to the level of 1.0 × 10 ¹³ Ω · cm, resulting in poor alignment of the liquid crystal.

Claims (4)

In the green photosensitive coloring composition used for the color filter for liquid crystal display devices which has a structure in which the colored pixels are in contact with the liquid crystal through the openings provided in the transparent conductive film, the green photosensitive coloring composition includes at least (a ) Transparent resin, (b) a polyfunctional monomer having three or more ethylenically unsaturated double bonds, (c) a photopolymerization initiator, (d) a colorant comprising a green pigment and a yellow pigment, and (e) a solvent. The transparent resin (a) has an acid value of 50 to 130 mg / g, and the volume resistivity of the hardened coating film of the green photosensitive coloring composition is 1.0 × 10 ¹⁴ Ω. -Green photosensitive coloring composition characterized by being cm or more.
(Here, the acid value is the content of acidic groups determined by an acid value reduction titration method using an aqueous potassium hydroxide (KOH) solution.) 2. The green photosensitive coloring according to claim 1, wherein the green pigment is a chlorinated brominated copper phthalocyanine pigment represented by the chemical formula (1) and containing an average of 15 bromine atoms in one molecule. Composition.

(In the formula (1), the central metal is copper, and 14.5 to 15.6 out of 16 X bonded to the four benzene rings on the outer periphery, and on average 15 are bromine atoms.) The green photosensitive coloring composition according to claim 1, wherein the transparent resin (a) contains an ethylenically unsaturated monomer represented by the following chemical formula (2) as a copolymerization component.

(In Formula (2), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a carbon atom that may contain a hydrogen atom or a benzene ring. Represents an alkyl group of 1 to 20. n represents an integer of 1 to 15.)   4. The color filter having at least a black matrix and a plurality of colored pixels on a transparent substrate and a pixel electrode in which a slit is provided on each pixel, wherein the green pixel is any one of claims 1 to 3. A color filter produced using the green photosensitive coloring composition described.