JP5564809B2 - Manufacturing method of color filter - Google Patents

Description

  The present invention relates to a blue coloring composition used for the production of a color filter used for a color liquid crystal display device, a color image pickup tube element, etc., a method for producing a color filter using this blue coloring composition, and a method for producing the same. Relates to the color filter.

The color filters that make up a liquid crystal display (LCD) are made by arranging two or more kinds of fine band (striped) filter segments of different hues in parallel or intersecting on the surface of a transparent substrate such as glass or the like. The filter segments are arranged in a constant vertical and horizontal arrangement. The filter segments are as small as several microns to several 100 microns in size, and are regularly arranged in a predetermined arrangement for each hue.
The filter segments that make up the color filter are activated by proximity exposure (ultraviolet light source exposure) through a photomask for pixel formation after applying a photosensitive material on a glass substrate, drying and removing excess solvent. It is formed by irradiating energy rays, curing (negative type) or increasing alkali solubility (positive type), and removing a portion that dissolves with an alkali solution or the like. By repeating this for each color of red, green and blue, for example, a color filter is produced.

In recent years, color liquid crystal display devices have formed a large market for liquid crystal color televisions, car navigation and liquid crystal display integrated laptops. Monitors and televisions for desktop computers that take advantage of energy saving and space saving features. As it has begun to spread. For this reason, it has attracted attention as a display device that replaces a conventional CRT (cathode ray tube television), but at present, the color reproduction characteristic of a liquid crystal display device is inferior to that of a CRT. Therefore, there is an increasing demand for high color reproducibility in color filters in which filter segments for each color are arranged.
In order to improve the color reproduction characteristics of the color filter, it is necessary to increase the pigment content in the colored composition or to increase the film thickness. However, in the method of increasing the pigment content, problems such as a decrease in sensitivity and deterioration in developability and resolution occur in the process of forming a filter segment by the photolithography method. In the method of increasing the film thickness, the exposure light does not reach the bottom of the film, causing problems such as the pattern shape of the filter segment being defective.

On the other hand, with the recent increase in the size of products using color filters, the size of photomasks for forming filter segments is inevitably increased, leading to an increase in manufacturing costs.
The commonly used proximity exposure method (ultraviolet light source exposure method) requires a large photomask that matches the substrate size in order to process a large substrate, but the laser exposure method reduces the size of the photomask. Alternatively, maskless is possible, and cost reduction can be expected.
Patent Document 1 discloses a curable composition using a semiconductor laser having a wavelength of 405 nm as an exposure light source.
Patent Document 2 discloses a curable composition using a laser device having a light source wavelength of less than 430 nm as an exposure light source.

However, in general, in a laser exposure method, when a colored coating film formed using a colored composition is exposed with a laser, the surface of the colored coating film is harder than the inside of the coating film. A difference in the degree of curing occurs, depending on the difference, the coating film surface peels off (a phenomenon in which only the cured coating film surface peels from the coating film when developing a colored coating film), and the coating film surface wrinkles (colored coating film) During baking after development, the coating film shrinks due to heat. However, due to the difference in the degree of curing, there are problems such as a phenomenon in which wavy wrinkles are generated on the coating film surface and adhesion to the substrate.
In particular, since the blue coloring composition containing a blue pigment strongly absorbs light in the wavelength region of 310 to 380 nm and has a very high absorbance, the above problem appears remarkably.
For this reason, it is important to obtain a blue colored composition having high sensitivity with light in a wavelength region of 310 to 380 nm.

Japanese Patent No. 3912405 Japanese Unexamined Patent Publication No. 2007-114602

  The present invention relates to a blue coloring composition applied to an exposure method using a laser having a wavelength of 310 to 380 nm as an exposure light source, and does not cause coating surface peeling and coating surface wrinkles, and so on. An object of the present invention is to provide a method for producing a color filter using such a blue coloring composition, and a color filter produced by such a method.

The method for producing a color filter of the present invention uses a blue coloring composition containing a blue pigment, a resin, a monomer having an ethylenically unsaturated double bond, an oxime ester photopolymerization initiator and a polyfunctional thiol on a substrate. A step of forming a blue coating film, a step of irradiating a region where the filter segment of the blue coating film is to be formed with a laser having a wavelength of 310 to 380 nm and curing, and a filter by removing an uncured portion of the blue coating film a method of manufacturing a color filter and a step of forming a segment, in the step of curing by irradiating the laser, the energy density per one pulse does not degrade the membrane of 0.01~150mJ / cm ² The laser is irradiated in a plurality of times .

According to the method for producing a color filter of the present invention, in the laser exposure method, even if the pigment content is high or the film thickness is thick, the filter segment having excellent pattern shape is free from peeling of the coating film surface and wrinkling of the coating film surface. Can be formed.
In addition, according to the method for producing a color filter of the present invention, by irradiating a laser with a specific wavelength for a short time, the blue coloring composition can be cured in a very short time, so using a small photomask, Alternatively, a filter segment having an excellent shape can be formed at a low cost without using a mask.
Furthermore, according to the present invention, a high-quality and inexpensive color filter is provided.

First, the blue coloring composition of the present invention will be described.
The blue coloring composition of the present invention irradiates a region of the blue coating film where a filter segment is to be formed with a laser having a wavelength of 310 to 380 nm using a blue coloring composition on the substrate. A blue coloring composition for use in a method for producing a color filter comprising: a step of curing and a step of forming a filter segment by removing an uncured portion of the blue coating film, wherein the blue pigment, resin, ethylene A blue coloring composition containing a monomer having a polymerizable unsaturated double bond, an oxime ester-based photopolymerization initiator, and a polyfunctional thiol.
Hereinafter, each component of the blue coloring composition of this invention is demonstrated.

(Blue pigment)
As the blue pigment, a commercially available pigment can be used, and a purple pigment can be used in combination according to the hue of the filter segment to be formed. As the blue pigment and the violet pigment, organic or inorganic pigments can be used alone or in admixture of two or more kinds, but it is particularly preferable to use an organic pigment having high color developability and heat resistance. The blue coloring composition of the present invention may be used in combination with a blue dye or a purple dye other than the pigment. Examples of the pigment include dyes and natural pigments.
Further, the organic pigment may be refined by salt milling, acid pasting or the like.

Hereinafter, specific examples of blue pigments and purple pigments that can be used in the blue coloring composition of the present invention are shown by color index numbers.
Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 80, etc., among which C.I. I. Pigment Blue 15: 6 is preferred.
The content of the blue pigment is usually preferably 1 to 80% by weight, more preferably 2 to 70% by weight, based on the solid content of the blue coloring composition (100% by weight). If the blue pigment content is less than 1% by weight, the film thickness of the color filter becomes excessively thick, which is not preferable, and if it exceeds 80% by weight, a good dispersion state cannot be obtained.

Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc., among which C.I. I. Pigment Violet 23 is preferred.
The content of the violet pigment is preferably 1 to 50% by weight, more preferably 1 to 40% by weight, based on the total amount of the pigment (total weight of the blue pigment and the violet pigment) in terms of color purity and contrast ratio.

(resin)
As the resin contained in the blue coloring composition, 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 can be used. The resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these can be used alone, but it is preferable to use a mixture of two or more.
Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like.
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, and a urea resin.

  As the photosensitive resin, a resin having an ethylenically unsaturated double bond is used. For example, an isocyanate group, an aldehyde group, or an epoxy group is added to a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group. A functional group having an ethylenically unsaturated double bond, such as a (meth) acryloyl group or a styryl group, by reacting a (meth) acrylic compound having a reactive substituent such as a carboxyl group or cinnamic acid. Introduced resin is mentioned. Specifically, a compound having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated double bond in a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group and an ethylenically unsaturated monomer Is obtained by reacting. Examples of the functional group capable of reacting with a hydroxyl group include an isocyanate group and a carboxyl group, but an isocyanate group is particularly preferred in terms of reactivity, and specifically, a compound having an isocyanate group and an ethylenically unsaturated double bond. , 2-acryloyl ethyl isocyanate, 2-methacryloyl ethyl isocyanate and the like. In addition, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

(Monomer having an ethylenically unsaturated double bond)
A monomer having an ethylenically unsaturated double bond is a component that is cured by irradiation with a laser having a wavelength of 310 to 380 nm.
Examples of monomers having an ethylenically unsaturated double bond include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tris. Various acrylic esters such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate and the like Examples include methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, acrylonitrile and the like. The monomer preferably has 4 to 12 ethylenically unsaturated double bonds, more preferably 6 to 12 from the viewpoint of increasing the sensitivity of the coloring composition. Monomers having an ethylenically unsaturated double bond can be used alone or in admixture of two or more.

The content of the monomer having an ethylenically unsaturated double bond is preferably 10 to 300 parts by weight, more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the pigment. When the monomer content is less than 10 parts by weight, the sensitivity is low. On the other hand, when the amount is more than 300 parts by weight, pattern shape linearity failure, tackiness or the like occurs.
The ratio (M / P) of the weight (M) of the monomer having an ethylenically unsaturated double bond to the weight (P) of the resin is preferably in the range of 0.10 to 3.00. .10 to 2.50 is more preferable, and 0.10 to 1.00 is particularly preferable. When the M / P is less than 0.10, the blue coating film hardly cures and a sufficient cured coating film cannot be obtained. If M / P is larger than 3.00, the vicinity of the surface of the coating film is markedly cured compared to the deep part of the coating film, so that the shape of the formed filter segment becomes an overhang shape or the linearity deteriorates. There is a case.

(Oxime ester photoinitiator)
As the oxime ester photopolymerization initiator, a compound represented by the following formula (1) or (2) is used.

[In Formula (1) and Formula (2), X _{1 to} X ₆ represent a hydrogen atom, a cyclic, linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group, and each alkyl group The phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, and a phenyl group. ]

The oxime ester photopolymerization initiator absorbs ultraviolet rays to cleave the N—O bond of the oxime, thereby generating an iminyl radical, a benzoyloxy radical, and an alkyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount.
In formula (1) and formula (2), examples of the linear or branched alkyl group having 1 to 12 carbon atoms of X _{1 to} X ₆ include a methyl group, an ethyl group, an n-propyl group, i- Propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n- A decyl group, n-undecyl group, n-dodecyl group, etc. are mentioned, As a cyclic alkyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example.

As the substituents for the alkyl and each phenyl group X ₁ to X _6, The alkoxyl group include a methoxy group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy, t -Butoxy group etc. are mentioned, As a halogen atom, a fluorine atom, a chlorine atom, etc. are mentioned, for example.
Each alkyl group and each phenyl group may be substituted with two or more substituents.
In Formula (1) and Formula (2), X ₁ is preferably a methyl group, an ethyl group, a phenyl group, or the like. X ₂ is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or i-propyl. Group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like are preferable, and as X ₃ , hydrogen atom, methyl group, ethyl group, n-propyl group and the like are preferable. preferable.
X ₄ , X ₅ and X ₆ are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group or the like.

  Specific examples of preferable compounds in the formula (1) of the present invention include 1- [4- (phenylthio) phenyl] -octane-1-one-2-oneoxime-O-acetate, 1- [4- (2-methyl) Phenylthio) phenyl] -octane-1-one-2-one oxime-O-acetate, 1- [4- (2,4,6-trimethylphenylthio) phenyl] -octane-1-one-2-one oxime-O -Acetate, 1- [4- (2-ethylphenylthio) phenyl] -octane-1-one-2-oneoxime-O-acetate, 1- [4- (phenylthio) phenyl] -octane-1-one-2 -Onoxime-O-benzoate, 1- [4- (2-methylphenylthio) phenyl] -octane-1-one-2-oneoxime-O-benzoate, 1 [4- (2,4,6-trimethylphenylthio) phenyl] -octane-1-one-2-oneoxime-O-benzoate, 1- [4- (2-ethylphenylthio) phenyl] -octane-1- On-2-one oxime-O-benzoate 1,2-octadion-1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] and the like.

  Moreover, as a specific example of the preferable compound in Formula (2) of this invention, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2,4,6-trimethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O -Acetyloxime) and the like.

Among these oxime ester photopolymerization initiators, 1,2-octadion-1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is particularly preferred.
In the present invention, the oxime ester photopolymerization initiator can be used by mixing with one or more other photopolymerization initiators.

  Other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Acetophenone photopolymerization initiators such as butan-1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Thioxanthone photopolymerization initiators such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s- Triazine, 2,4-bis (trick (Romethyl) -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′-methoxystyryl) -6-triazine, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used.

Content of a photoinitiator can be used in the quantity of 1-100 weight part with respect to 100 weight part of pigments, Preferably it is 3-50 weight part. When the content of the photopolymerization initiator is less than 1 part by weight, the sensitivity is low. On the other hand, when the amount is more than 100 parts by weight, heat resistance and light transmittance are deteriorated.
The ratio (I / M) of the weight (I) of the photopolymerization initiator to the weight (M) of the monomer having an ethylenically unsaturated double bond is preferably in the range of 0.01 to 1.00. 0.02 to 0.90 is more preferable, and 0.05 to 0.50 is particularly preferable. If I / M is less than 0.01, the coating film may not be cured. On the other hand, when it is larger than 1.00, the transmittance of the blue coating film may be lowered, and heat resistance and solvent resistance may be inferior.

  A sensitizer can be used in combination with the photopolymerization initiator. Examples of the sensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate. Ethyl acetate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4 Amine compounds such as 4,4′-bis (diethylamino) benzophenone and 4,4′-bis (ethylmethylamino) benzophenone. These sensitizers can be used individually by 1 type or in mixture of 2 or more types. The content of the sensitizer is preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

(Multifunctional thiol)
The polyfunctional thiol contained in the blue coloring composition of the present invention may be a compound having two or more thiol (SH) groups.
By using a polyfunctional thiol together with the above-mentioned photopolymerization initiator, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation. Becomes high sensitivity. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable. Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu Arylamino) -4,6-dimercapto--s- triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tris thiopropionate, pentaerythritol tetrakis thiopropionate.

These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the pigment. If the polyfunctional thiol content is less than 0.05 parts by weight, the effect of the chain transfer agent is small, and if it is more than 100 parts by weight, the polymerization initiating function is not improved, and developability, adhesion, etc. are insufficient. .

(Optional component)
The blue colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.
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 0.1 to 10 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

It is easy to form a filter segment by sufficiently dispersing the pigment in the blue colored composition and applying it on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to do so, a solvent can be included.
Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,5,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol , 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ -Butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol Ether monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, Cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether Ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene Glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexane SANOL acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic esters, and the like, used alone or in combination.

  When dispersing the pigment in the resin, a dispersant such as a surfactant, a resin-type pigment dispersant, and a dye derivative can be appropriately used. The dispersant is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition is used in which the pigment is dispersed in a resin and an organic solvent using the dispersant. Provides a color filter excellent in transparency. The pigment dispersant can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

  Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate. , Anionic surface activity such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Agents: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxy Nonionic surfactants such as ethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethyl Examples include amphoteric surfactants such as alkylbetaines such as aminoacetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

  Resin-type pigment dispersants are resins that have a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the transparent resin, and stabilize the dispersion of the pigment into the transparent resin by adsorbing to the pigment. It works to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they 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 SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 3184, manufactured by Japan Lubrizol Corporation 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400405, manufactured by Efka Chemicals 402, 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. Such organic dyes also 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 alone or in combination of two or more.

(Production method of blue coloring composition)
The blue coloring composition of the present invention is obtained by finely dispersing a blue pigment in various resins such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor in a resin and a solvent together with the pigment dispersant as necessary. And a polyfunctional thiol, a monomer having an ethylenically unsaturated double bond, and an oxime ester photopolymerization initiator. Moreover, the coloring composition containing 2 or more types of pigments can also be manufactured by mixing each pigment separately finely dispersed in a resin and a solvent.

The blue-colored composition of the present invention is prepared by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more It is preferable to remove the dust.
Next, a method for manufacturing the color filter of the present invention will be described.
The method for producing a color filter of the present invention includes a step of forming a blue coating film on a substrate using the blue coloring composition, and a laser having a wavelength of 310 to 380 nm in a region where the filter segment of the blue coating film is to be formed. And a step of removing the uncured portion of the blue coating film to form a filter segment.

Hereinafter, each step will be described.
(Blue film formation process)
In the blue coating film forming step, the blue coloring composition of the present invention is applied by spin coating or die coating, and an excess solvent is removed as necessary to form a blue coating on the substrate.
Color filter substrates include glass plates such as soda-lime glass, low alkali borosilicate glass, and non-alkali aluminoborosilicate glass that have a high transmittance for visible light, and resins such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. A plate is used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

(Exposure and curing process)
In the exposure / curing step, the filter segment formation planned region of the blue coating film is irradiated with a laser having a wavelength of 310 to 380 nm to be cured. Specifically, a blue coating film formed on a large-sized substrate is irradiated with a laser through a photomask that is smaller than the substrate to cure a portion that becomes a filter segment of the blue coating film.
A laser wavelength of 343 nm and 355 nm is particularly used for a solid (YAG) laser, 351 nm (XeF) is particularly used for an excimer laser, and 375 nm is particularly used for a semiconductor laser. Among these, 355 nm is more preferable from the viewpoints of stability and cost. The energy density per pulse of the laser used in the present invention is preferably 0.01 to 150 mJ / cm ² , and the laser can be applied to the blue coating film once or a plurality of times. It is essential that the blue coating is cured by applying a weak energy that does not decompose the film.

(Uncured part removal process)
In the uncured portion removing step, the uncured portion of the blue coating film is removed to form a filter segment. When removing the uncured portion, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like 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.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  The color filter according to the present invention includes the blue filter segment manufactured by the above method, but may further include at least one color filter segment selected from red, green, yellow, and magenta. Each color filter segment other than blue can be formed using each color coloring composition containing a pigment, a resin, a monomer having an ethylenically unsaturated double bond, a photopolymerization initiator, and the like.

  Examples of the red coloring composition include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, H.264, 272, C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73, etc., and C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 A composition obtained by using such 181,182,185,187,188,193,194,198,199,213,214.

Examples of the green coloring composition include C.I. I. Pigment Green 7, 10, 36, 37, 58 and the like, and a composition obtained by using the above yellow pigment for toning as required.
The yellow coloring composition is a composition obtained using the yellow pigment.
Examples of magenta colored compositions include C.I. I. Pigment Violet 1, 19, C.I. I. Pigment Red 81, 144, 146, 177, 169, and the like, and a composition obtained by using the above-mentioned yellow pigment for toning as required.

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the examples and comparative examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.
First, preparation of acrylic resin solutions and pigment dispersions used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

(Preparation of acrylic resin solution)
370 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour 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 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 solution was obtained.
After cooling to room temperature, about 2 g of acrylic resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Based on the measurement result, the previously synthesized acrylic resin solution has a non-volatile content of 20%. Thus, cyclohexanone was added to prepare an acrylic resin solution. The weight average molecular weight Mw of the obtained acrylic resin was 40000.

(Preparation of pigment dispersion)
A mixture having the composition shown in Table 1 below is uniformly stirred and mixed, dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, filtered through a 5 μm filter, and blue pigment dispersions B-1 and B-2 Was prepared.

PB15: 6: ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6)
(BASF "Heliogen Blue L-6700F")
PV23: Dioxazine-based purple pigment (CI Pigment Violet 23)
("Fast Violet RL" manufactured by Clariant)
Pigment dispersant: “Solsperse 20000” manufactured by Nippon Lubrizol
Resin solution: previously prepared acrylic resin solution Organic solvent: cyclohexanone

[Examples 1-15, Comparative Examples 1-6]
The mixture of the formulation shown in Table 2 including the pigment dispersion B-1 or B-2 prepared above was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue colored composition BR- 1-BR-17 was obtained.

Pigment dispersion: previously prepared pigment dispersion resin solution: previously prepared acrylic resin solution Monomer: “Aronix M-402” manufactured by Toagosei Co., Ltd.
Photopolymerization initiator: Photopolymerization initiator polyfunctional thiol SA shown in Table 3 below: Trimethylolpropane tristhiopropionate polyfunctional thiol SB: Ethylene glycol bisthiopropionate Organic solvent: cyclohexanone

[Filter segment pattern formation]
Each obtained blue coloring composition was applied on a 10 cm × 10 cm glass substrate with a spin coater to a thickness of about 2 μm, and left in an oven at 70 ° C. for 15 minutes to remove excess solvent and dry. Next, a striped photomask having a thickness of 100 μm was set from the colored composition coating film at an interval of 150 μm, and a laser of a laser light source type shown in Table 4 below was irradiated so that the exposure amount was 30 mJ / cm ² . The exposure dose was measured using “PE10B-V2” manufactured by OPHIR.
Further, the unexposed portion was removed by spray development with a developer composed of a 0.2% sodium carbonate aqueous solution, and then washed with ion-exchanged water. The substrate was heated at 230 ° C. for 30 minutes to form a filter segment. .

Multifunctional thiol SA: Trimethylolpropane tristhiopropionate SB: Ethylene glycol bisthiopropionate Laser source LA: Solid (YAG) laser, wavelength 343 nm
LB: (XeF) excimer laser, wavelength 351 nm
LC: Solid state (YAG) laser, wavelength 355 nm
LD: Semiconductor laser, wavelength 375 nm

The filter segment formed using the blue coloring composition obtained in the examples and comparative examples was observed using an optical microscope, and the coating film surface peeling and coating film surface wrinkles were evaluated according to the following criteria. The results are shown in Table 4.
(1) Surface peeling ○: No peeling ○ △: Slight peeling (practical level)
Δ: Partially peeled ×: Peeled over the entire coating film (2) Surface wrinkle ○: No wrinkle (coating film surface is smooth)
Δ: Minor wrinkles (a level where there is no practical problem)
×: Wrinkles on the entire surface (wrinkles are generated on the entire coating surface)

  As shown in Table 4 above, in Examples 1 to 15, although there are some differences depending on the formulation of the blue coloring composition, all of the coating surface peeling and coating surface wrinkles are practically inferior filter segments. It was. On the other hand, in the blue coloring compositions of Comparative Examples 1, 2, and 6, the coating film was peeled off and the coating surface wrinkle could not be evaluated. Moreover, in the blue coloring composition of Comparative Examples 3, 4, and 5, the coating film surface wrinkles occurred, and a good filter segment was not obtained.

Claims (2)

Forming a blue coating film on a substrate using a blue coloring composition containing a blue pigment, a resin, a monomer having an ethylenically unsaturated double bond, an oxime ester photopolymerization initiator and a polyfunctional thiol ; and A color comprising: a step of forming a filter segment of a blue coating film by irradiating and curing a laser having a wavelength of 310 to 380 nm; and a step of forming a filter segment by removing an uncured portion of the blue coating film A method for manufacturing a filter, comprising:
In the step of irradiating and curing the laser, a laser that does not decompose a film having an energy density of 0.01 to 150 mJ / cm ² per pulse is irradiated in a plurality of times . Manufacturing method . The method for producing a color filter according to claim 1, wherein the oxime ester photopolymerization initiator is a compound represented by the following formula (1) or (2).
[In the formulas (1) and (2), X1 to X6 represent a hydrogen atom, a cyclic, linear or branched alkyl group having 1 to 12 carbon atoms, or a phenyl group. The group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, and a phenyl group. ]