JP2008209749A - Colored polymerizable composition for color filter, color filter and method for manufacturing the same, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a colored pattern excellent in solvent resistance and adhesion to a support and to suppress the generation of development residues, when recoating is carried out on an existing colored pattern by slit coating to form colored patterns of a plurality of colors. <P>SOLUTION: A colored polymerizable composition for a color filter used for coating by a slit method comprises a colorant, a carboxyl group-containing binder, a photopolymerizable compound, a compound having a blocked isocyanate group, a photopolymerization initiator and a solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a colored polymerizable composition for a color filter suitable for producing a color filter using a slit method, a color filter using the same, a method for producing the same, and a display device.

  The color filter is an essential component for a liquid crystal display. Since a liquid crystal display is more compact than a CRT as a display device and has the same or better performance, in recent years it has tended to replace the CRT as a display device used in the display screens of televisions, personal computers, and other devices. is there.

  As a method for producing a color filter, a photosensitive colored resin composition is applied on a substrate provided with a black matrix to form a coating film, and the formed coating film is exposed and developed to form a pattern. , Red (R), green (G), blue (B) and the like, which are repeatedly performed according to the desired number of hues, are widely used.

  As a colored resin composition used for the production of a color filter, a specific polymerizable compound and a specific heteroalicyclic block isocyanate compound can be used as a composition capable of forming a resin cured product having solvent resistance and peeling liquid resistance. There is known a photothermally polymerizable composition using the above (for example, see Patent Document 1). Moreover, the photosensitive resin composition used for the photosensitive film for metal precision processing is also known as a photosensitive resin composition containing a block isocyanate compound (for example, refer patent document 2).

  On the other hand, the substrate size tends to increase with the increase in the screen size of the display device, and the application of the colored resin composition is liquid-saving and manufacturing efficiency, etc. compared to the conventional spin application, compared with spin application. Slit coating that excels in the quality has become the mainstream.

  Slit coating is (1) less liquid loss than spin coating, (2) less spraying of coating solution, reducing cleaning treatment, and (3) re-mixing of scattered liquid components into coating film There are no advantages such as (4) no tapping time since rotation is not stopped, and (5) easy application to a large substrate. From these advantages, slit coating is suitable for producing a color filter for a large display screen, and is expected as an advantageous coating method.

As a colored resin composition used for slit coating, a colored photosensitive resin composition having a viscosity satisfying a predetermined condition is known, and a coating film with good uniformity is obtained (for example, Patent Documents). 3).
JP 2006-119441 A Japanese Patent Laid-Open No. 10-148938 JP 2005-49828 A

  However, in the case of slit coating, the amount of residual solvent is larger than that of spin coating, and when the existing polymerizable pattern is applied on top of the existing pattern formed, the existing pattern is contained in the composition. The time in contact with the solvent increases. When the contact time of the solvent with the existing pattern becomes longer, lifting of the existing pattern, that is, lifting from the support is likely to occur, and there is a problem that the adhesion between the existing pattern and the support on which the existing pattern is formed deteriorates. is there. In addition, display unevenness may occur due to unevenness (penetration unevenness) due to the penetration into the existing pattern.

  In addition, in the case of slit coating, it is generally necessary to adjust the solid content concentration to a relatively thin range of 20% or less from the point of applicability, compared with the case of using a spin coating solution (solid content concentration around 25%). , Lifting (adhesiveness) and display unevenness during overcoating are likely to occur.

  On the other hand, when a compound having a blocked isocyanate group is used in the colored polymerizable composition, there is also a problem that a development residue is easily generated.

  The present invention has been made in view of the above, and has excellent solvent resistance and adhesion to a support when multiple colored patterns are formed by overcoating by slit coating on an existing colored pattern. Colored polymerizable composition for color filter that can form a high colored pattern and development residue is suppressed, color that has good adhesion to the support and display unevenness when displaying images It is an object to provide a filter, a manufacturing method thereof, and a display device in which display unevenness is suppressed, and to achieve the object.

Specific means for achieving the above object are as follows.
<1> (A) a colorant, (B) a carboxyl group-containing binder, (C) a photopolymerizable compound, (D) a compound having a blocked isocyanate group, (E) a photopolymerization initiator, and (F) a solvent. It is a colored polymerizable composition for color filters that is contained and used for coating by the slit method.
<2> The colored polymerizable composition for a color filter according to <1>, wherein the compound (D) having a blocked isocyanate group has two or more blocked isocyanate groups.
<3> The color filter according to <1> or <2>, wherein at least one of the solvents (F) is propylene glycol monomethyl ether acetate, and the solid content is 5 to 20% by mass. Coloring polymerizable composition for use.

<4> A color filter produced by forming a colored pattern using the colored polymerizable composition for a color filter according to any one of <1> to <3>.
<5> On the support, a coating film forming step of forming a colored film by applying the colored polymerizable composition for a color filter according to any one of the above <1> to <3> by a slit method; A process group including an exposure process for exposing the coated colored film and a developing process for developing the exposed colored film is repeated at least twice, and a plurality of colored patterns are sequentially formed on the same support. It is a manufacturing method of the color filter to form.
<6> A display device comprising the color filter according to <4> or the color filter produced by the method for producing a color filter according to <5>.

According to the present invention, it is possible to form a colored pattern having excellent solvent resistance and high adhesion to a support when a plurality of colored patterns are formed by overcoating by slit coating on an existing colored pattern. Thus, it is possible to provide a colored polymerizable composition for a color filter in which the generation of development residues is suppressed. Also,
ADVANTAGE OF THE INVENTION According to this invention, the adhesiveness with a support body is favorable, the color filter by which the generation | occurrence | production of the display nonuniformity at the time of image display was suppressed, its manufacturing method, and the display apparatus by which the generation | occurrence | production of the display nonuniformity was suppressed are provided. can do.

  Hereinafter, the colored polymerizable composition for a color filter of the present invention, a color filter using the same, a manufacturing method thereof, and a display device will be described in detail.

<Coloring polymerizable composition for color filter>
The colored polymerizable composition for a color filter of the present invention includes (A) a colorant, (B) a carboxyl group-containing binder, (C) a photopolymerizable compound, (D) a compound having a blocked isocyanate group, and (E) photopolymerization. It comprises at least an initiator and a solvent (F), and may be constituted using other components as required.

  In the colored polymerizable composition for a color filter of the present invention, the contact time with a solvent that tends to remain at the time of slit coating is increased by using a compound having a blocked isocyanate group (D) when used for slit coating. As a result, lifting of the existing pattern (for example, colored pixels) from the support (lifting) and soaking unevenness are suppressed, and the occurrence of development residue during development is also suppressed. A colored pattern with high adhesion can be obtained, and thus a color filter in which display unevenness is prevented can be obtained.

Hereinafter, the constituent components of the colored polymerizable composition for a color filter of the present invention will be described in detail.
(A) Colorant The colored polymerizable composition for a color filter of the present invention contains at least one colorant. By containing a colorant, the colored polymerizable composition for a color filter of the present invention can be used for forming colored pixels, a black matrix, and the like constituting the color filter.

  The colorant can be selected from conventionally known various pigments, dyes and the like. A coloring agent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  As the pigment, various conventionally known inorganic pigments or organic pigments can be used. Further, since it is preferable that the pigment has a high transmittance when it is contained, it is desirable that the pigment has a particle size as small as possible. However, in consideration of handling properties, a pigment having an average particle size of 0.01 μm to 0.1 μm is preferable. The pigment is preferably 0.01 μm to 0.05 μm.

  Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. And composite oxides of the above metals.

  Examples of the organic pigment include CIPigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199 CIPigment Orange 36, 38, 43, 71; CIPigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177,209, 220, 224, 242, 254, 255, 264, 270; CI Pigment Violet 19, 23, 32, 39; CIPigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; CIPigment Green 7, 36, 37; CIPigment Brown 25, 28; CIPigment Black 1, 7;

  In the present invention, those having a basic N atom in the structural formula of the pigment are particularly preferred. A pigment having a basic N atom exhibits good dispersibility in the composition. Although the cause is not fully elucidated, it is presumed that the good affinity between the photopolymerization component and the pigment has an effect.

  Among the above-mentioned various pigments, more preferable pigments are CIPigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; CIPigment Orange 36, 71; CIPigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264; CIPigment Violet 19, 23, 32; CIPigment Blue 15: 1, 15: 3, 15: 6, 16, 22 , 60, 66; CIPigment Black 1. However, it is not limited to these.

The organic pigments can be used alone or in combination of a plurality of types in order to improve color purity. Specific examples of combinations are shown below.
Examples of red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments, and perylene red pigments. A mixture of these is used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 is C.I. as a perylene pigment. I. Pigment red 155, C.I. I. Pigment Red 224 is C.I. as a diketopyrrolopyrrole pigment. I. Pigment red 254, and C.I. I. Pigment yellow 83 or C.I. I. Good mixing with Pigment Yellow 139.
The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. When the mass ratio of the red pigment to the yellow pigment is within the above range, the light transmittance of 400 to 500 nm can be suppressed, the color purity can be increased, and the main wavelength does not become a short wavelength. The deviation from the target hue is small. Moreover, about mass ratio of a red pigment and a yellow pigment, 100: 10-100: 30 is especially preferable. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment alone or at least one of them is mixed with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment, for example, C . I. Pigment green 7, C.I. I. Pigment green 36 or C.I. I. Pigment green 37, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixture with CI Pigment Yellow 185 is preferred.

  The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. When the mass ratio is within the above range, the light transmittance of 400 to 450 nm can be suppressed, the color purity can be increased, the main wavelength does not become a long wavelength, and the deviation from the NTSC target hue does not occur. small. A more preferred mass ratio is in the range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine pigment alone or a mixture of at least one phthalocyanine pigment and a dioxazine violet pigment is used. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Furthermore, by using a powdered processed pigment in which the pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, or the like, photothermal polymerization with good dispersibility and dispersion stability. A composition can be obtained.

  In addition, the colored polymerizable composition for a color filter according to the present invention forms a black matrix by using a colorant using black carbon, titanium carbon, iron oxide, titanium oxide or the like alone or in combination. It is also possible to do.

As the pigment, a pigment coated with a pigment coating resin can also be used. Examples of the pigment coating resin include a resin such as an acrylic resin containing a carboxyl group. Examples of the acrylic resin containing a carboxyl group include monomers having a carboxyl group such as (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, styrene, α-methylstyrene, ( Methyl) methacrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, Allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonic acid ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol acrylamide, N, N dimethyl acrylamide, N-methyl Acryloyl morpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl acrylamide, copolymerizable component and, obtained by copolymerizing a polymer such.
Among them, preferred is an acrylic resin containing at least (meth) acrylic acid or (meth) acrylic acid alkyl ether as a constituent monomer, and more preferred is an acrylic resin containing (meth) acrylic acid and styrene.

  In addition, these resins may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and an ethylenic double bond can be added to the resin side chain. By imparting a double bond to the resin side chain, the photocurability is increased, so that the resolution and adhesion can be further improved. However, if a resin having a double bond in the side chain is used, the regularity of the cured product may be changed and the dielectric constant may be increased.

  Examples of the synthesis means for introducing an ethylenic double bond include the methods described in JP-B-50-34443 and JP-B-50-34444. Specifically, a method of reacting a compound having both a glycidyl group, an epoxycyclohexyl group, and a (meth) acryloyl group with a carboxyl group or a hydroxyl group, acrylic acid chloride, and the like can be given. For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By using a compound such as acrylic acid chloride or (meth) allyl chloride and reacting with a resin having a carboxyl group or a hydroxyl group, a resin having a polymer group in the side chain can be obtained.

In general, a dispersant can be used for dispersing the organic pigment, carbon, and the like.
As the dispersant, the pigment coating resin can be used as it is, or a dispersant described later can be used in combination. These dispersants can be used in combination of a plurality of types in addition to a single type. By the dispersion treatment, the resin is adsorbed on the pigment surface, and at the same time, the aggregation of the pigment particles is destroyed and the particle size can be refined.
As the dispersant, Anti-Terra-U, Disperbyk-160, 161, 162, 163 manufactured by BYK, Solspers 20000, 24000GR, 26000, 28000, DA-703 manufactured by Enomoto Kasei Co., Ltd. -50, NDC-8194L, NDC-8203L, NDC-8257L, KS-860, Kagen's homogenal L-18, L-1820, L-95, L-100, VP5000 made by Nippon Paint Examples thereof include known dispersion resins such as E5703P manufactured by Goodrich, VAGH manufactured by Union Carbide, UR8200 manufactured by Toyobo, and MR113 manufactured by Nippon Zeon.

  Further, phthalocyanine derivatives (trade name: EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90 , No. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl Nonionic surfactants such as ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; F-top EF301, EF303, EF352 (made by Shin-Akita Kasei Co., Ltd.), Megaf F171, F172, F173 (Dainippon Ink & Chemicals), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC-101, SC-102, SC -103, SC-104, SC-105, SC-1068 (manufactured by Asahi Glass Co., Ltd.), etc .; anionic surfactants such as W004, W005, W017 (manufactured by Yusho Co., Ltd.); EFKA- 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid Polymer dispersing agents such as 9100 (manufactured by San Nopco); Various sparse dispersions such as Sparse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. (manufactured by Geneca); Adeka Pluronic L31, F38, L42 L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P123 (Asahi Denka) And Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.).

When a dye is contained as the colorant, it is preferable to obtain a colored polymerizable composition for a color filter that is uniformly dissolved in the composition.
There is no restriction | limiting in particular as said dye, A conventionally well-known dye can be used for a color filter use conventionally. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  Chemical structures include pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene , Phthalocyanine, benzopyran, and indigo dyes can be used.

  The content of the colorant in the color polymerizable composition for a color filter is preferably 20 to 80% by mass, more preferably 25 to 65% by mass, based on the total solid content of the composition. When the content of the colorant is within the above range, color characteristics with high chromaticity and good light shielding properties can be obtained.

(B) Carboxyl group-containing binder The colored polymerizable composition for a color filter of the present invention contains at least one carboxyl group-containing binder. Since the binder in the present invention has a carboxyl group, the composition can be constituted to be alkali-soluble, and an unnecessary pattern can be removed using an alkaline developer to form an arbitrary pattern.

  The carboxyl group-containing binder can be appropriately selected from known binders having a carboxyl group. Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated polycarboxylic acids having at least one carboxyl group in the molecule, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids. Etc.

  Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

  The unsaturated polyvalent carboxylic acid may be its acid anhydride. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryloyloxyethyl). , Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like.

  The unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.

  A carboxyl group-containing monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

Among the above, an acrylic copolymer is preferable in the present invention.
Examples of the acrylic copolymer include a copolymer of a carboxyl group-containing monomer (particularly an acryloyl group-containing monomer) and another monomer copolymerizable with the monomer.

Examples of other monomers copolymerizable with the carboxyl group-containing monomer include:
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene;

  Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl Methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl Acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Tyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, Toxipropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy- Unsaturated carboxylic esters such as 3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate;

  2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated alkylaminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate;

Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples include polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polysiloxane, etc. be able to.
These monomers may be used alone or in combination of two or more.

  The ratio of the carboxyl group-containing monomer unit in the carboxyl group-containing binder is a mass fraction, usually 10 to 50% by mass, preferably 15 to 40% by mass, and more preferably 25 to 40% by mass. When the ratio of the carboxyl group-containing monomer unit is within the above range, the solubility in the developer is good, and the pattern tends to be formed accurately during development.

  Examples of the acrylic copolymer include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxy. Ethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) Acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, ( (Meth) acrylic acid / 2-hydroxye (Meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer , (Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / benzyl (meth) acrylate / N -Phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / benzyl (meth) Acrylate / N-phenylmale De / styrene / glycerol mono (meth) acrylate copolymer, and the like.

"
Here, (meth) acrylate means representing acrylate or methacrylate (the same applies hereinafter).

  Among the above, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer (Meth) acrylic acid / methyl (meth) acrylate / styrene copolymer is preferred.

  The weight average molecular weight (polystyrene conversion) of the carboxyl group-containing binder is usually 1,000 to 100,000, preferably 2,000 to 80,000, more preferably 3,000 to 70,000, More preferably, it is 5,000-50,000. When the molecular weight of the carboxyl group-containing binder is within the above range, the coating film hardness is improved, the unexposed area after development has good solubility in the developer and a high residual film ratio is obtained, and a colored pattern with higher resolution is obtained. Can be formed.

As an acid value of a carboxyl group-containing binder, it is 50-150 normally, and the range of 60-140 is preferable. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution. .
Especially, as for an acid value, 80-135 are more preferable, More preferably, it is 80-130. When the acid value is within the above range, the solubility in the developer is improved, the unexposed part is easily dissolved and the sensitivity can be increased, and the remaining film ratio of the exposed part (cured part) can be further improved. .

  (B) As content in the colored polymerizable composition for color filters of a carboxyl group-containing binder, 1-50 mass% is preferable with respect to the total solid of the colored polymerizable composition for color filters, and 5-40 The mass% is more preferable. (B) When the content of the carboxyl group-containing binder is within the above range, a uniform coating film and a uniform pattern can be obtained.

(C) Photopolymerizable compound The colored polymerizable composition for a color filter of the present invention contains at least one photopolymerizable compound. The photopolymerizable compound is a compound that can be polymerized by an active radical or an acid generated from a photopolymerization initiator (E) described later by light irradiation. Examples of the photopolymerizable compound include compounds having a polymerizable carbon-carbon unsaturated bond.

  As the photopolymerizable compound, a known photopolymerizable compound can be used without particular limitation. As the photopolymerizable compound, a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable. It is more preferable that it is a (meth) acryl compound. From the viewpoint of sensitivity and high curing, the photopolymerizable compound is more preferably a polyfunctional (meth) acrylic compound.

  Examples of photopolymerizable compounds include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, Methylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Hexanediol di (meth) acrylate,

Trimethylolpropane tris (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanurate, and (meth) acrylated after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as glycerin and trimethylolethane, Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof described in JP-B 52-30490 It is possible . Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 can be listed as photocurable monomers and oligomers.

  The content of the photopolymerizable compound in the colored polymerizable composition for a color filter is preferably 1 to 60% by mass and more preferably 10 to 50% by mass in the total solid content. When the content is 1% by mass or more, curing of the exposed portion proceeds favorably, and when it is 60% by mass or less, the elution property of the unexposed portion is improved.

(D) Compound having a blocked isocyanate group The colored polymerizable composition for a color filter of the present invention contains at least one compound having a blocked isocyanate group (hereinafter sometimes referred to as “block isocyanate group-containing compound”). . In the present invention, by containing the blocked isocyanate group-containing compound, when further applied on a support having an existing pattern (for example, colored pixels) by the slit method, the floating (lifting) from the support of the existing pattern and Soaking unevenness can be suppressed, and development residues during subsequent development can also be suppressed. Further, the block is removed by heating after development, and a better degree of curing is obtained. As a result, a color pattern and a display device that are fine, have high solvent resistance, and have excellent adhesion to the support, and thus display unevenness can be produced.

  The blocked isocyanate group is obtained by blocking an isocyanate group which is a reactive group in the compound.

  The blocked isocyanate group-containing compound is obtained by reacting the isocyanate group of the isocyanate group-containing compound with a blocking agent. Examples of the blocked isocyanate group-containing compound in the present invention include compounds in which the following isocyanate compounds are blocked with a blocking agent.

  Examples of the isocyanate group-containing compound include monofunctional isocyanate compounds such as ethyl isocyanate, n-propyl isocyanate, i-propyl isocyanate, and butyl isocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3′-dimethoxy-biphenyl diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, Xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, 4-chloroxylylene-1,3-diisocyanate, 2-methylxylylene-1,3-dii Cyanate, 4,4′-diphenylpropane diisocyanate, 4,4′-diphenylhexafluoropropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1 , 2-diisocyanate, cyclohexylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane and 1,3-bis ( And bifunctional isocyanate compounds such as isocyanate methyl) cyclohexane, isophorone diisocyanate, and lysine diisocyanate. Furthermore, addition reaction products of these bifunctional isocyanate compounds with bifunctional alcohols such as ethylene glycols and bisphenols and phenols can also be used.

  Furthermore, a polyfunctional isocyanate compound can also be used. As an example of such a compound, the above-mentioned bifunctional isocyanate compound is used as a main raw material, and these trimers (burette or isocyanurate), trimethylolpropane, and other polyols and polyfunctional isocyanate compounds are added as an adduct. , A formalin condensate of benzene isocyanate, a polymer of an isocyanate compound having a polymerizable group such as methacryloyloxyethyl isocyanate, lysine triisocyanate, toluene-2,4,6-triisocyanate, 4,4 ′, 4 ″ -tri Tetravalent isocyanates such as phenylmethane triisocyanate and 4,4′-dimethyldiphenylmethane-2,2 ′, 5,5′-tetraisocyanate can also be used.

  These compounds are described in “Polyurethane Resin Handbook” (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987)).

  Further, as the blocking agent for isocyanate groups, those capable of regenerating isocyanate groups by heating can be selected. For example, phenols such as phenol and cresol, oxime compounds such as methyl ethyl ketoxime, acetone oxime, cyclohexanone oxime, lactam compounds such as ε-caprolactam, γ-butyrolactam, β-propiolactam, ethyl acetoacetate, diethyl malonate Active methylene compounds such as acetylacetone, amine compounds such as aniline and diphenylamine, imidazole compounds such as imidazole and benzimidazole, azole compounds such as benztriazole, imide compounds such as N-hydroxyimide and phthalimide, etc. A blocking agent can be used.

  Among the above-mentioned blocked isocyanate group-containing compounds, bifunctional compounds having two or more blocked isocyanate groups in one molecule are preferable. When two or more blocked isocyanate groups are contained in one molecule, it is effective for the effect of preventing lifting of an existing pattern by a solvent, and better curability and support adhesion can be obtained.

  Among the blocked isocyanate group-containing compounds having two or more blocked isocyanate groups, in particular, xylene diisocyanate and hydrogenated products thereof, aliphatic isocyanates such as hexamethylene diisocyanate, dimers or trimers thereof (burettes or trimers). A block isocyanate compound made of a polyfunctional compound as an adduct with a polyol such as isocyanurate) or trimethylolpropane is preferred.

  The number of blocked isocyanate groups in one molecule is preferably 2 or more, particularly preferably 2 to 3, for the above reason.

  (D) As content in the colored polymerizable composition for color filters of a block isocyanate group containing compound, 1-50 mass% is preferable with respect to the total solid, and 2-25 mass% is more preferable. When the content is within the above range, the effect of suppressing lifting and solvent soaking (soaking unevenness) and the effect of suppressing development residue can be further improved.

(E) Photopolymerization initiator The colored polymerizable composition for a color filter of the present invention contains at least one photopolymerization initiator.
A conventionally well-known thing can be used as said photoinitiator. For example, active halogen compounds such as halomethyloxadiazole compounds described in JP-B-57-6096, halomethyl-s-triazines described in JP-B-59-1281 and JP-A-53-133428, etc. Aromatic carbonyl compounds such as ketals, acetals and benzoin alkyl ethers described in U.S. Pat. No. 4,318,791 and European Patent No. 88050A, and fragrances such as benzophenones described in U.S. Pat. No. 4,199,420. Group ketone compounds, (thio) xanthones, acridine compounds described in French Patent 2456741, coumarins, lophine dimer compounds described in JP-A-10-62986, JP-A-8-15521 And the described sulfonium organoboron complexes.

  Specifically, an acetophenone initiator (for example, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, etc.), ketal initiators (eg, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, etc.), benzophenone initiators (eg, benzophenone, 4 , 4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, 1-hydroxy-cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl)- Tanone-1,2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 etc. ), Benzoin and benzoyl initiators (eg, benzoin propyl ether, benzoin butyl ether, benzoin methyl ether, methyl-o-benzoyl benzoate, etc.),

Xanthone-based initiators (diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, etc.), triazine-based initiators (for example, 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine 2,4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2, 6-di (trichloromethyl) -s-triazine, methoxystyryl 2,6-di (trichloromethyl) -s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -S-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (Diethoxycarbonylamino) phenyl) -2,6-di (chloromethyl) -s-triazine etc.),

Halomethyloxadiazole initiators (for example, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodi Azole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole Etc.), acridine-based initiators (for example, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, etc.), coumarin-based initiators (for example, 3-methyl-5-amino-((s-triazine- 2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl- -Dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin and the like), lophine dimer initiators (for example, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer) 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl)- 4,5-diphenylimidazolyl dimer, etc.), 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophospho-tria Kill phenyl sulfonium salts, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl distearate disulfide, and the like.

  As content in the colored polymerizable composition for color filters of a photoinitiator, 0.5-60 mass% is preferable with respect to the quantity of the said (C) photopolymerizable compound, and 1-50 mass%. preferable. When the content is within the above range, the polymerization reaction is not inhibited and the film strength can be prevented from being lowered.

(F) Solvent The colored polymerizable composition for a color filter of the present invention contains at least one solvent. By containing the solvent, various components can be dissolved or dispersed to prepare a liquid coating solution.

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. 3-methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate and ethyl 3-oxypropionate Oxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), methyl 2-oxypropionate, 2-oxypropio 2-oxypropionic acid alkyl esters such as ethyl acid, propyl 2-oxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate Etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol propyl ether acetate, etc .;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons such as toluene and xylene.

  As the solvent in the present invention, in terms of coating suitability and drying suitability, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, It is preferable to use at least one selected from 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate (PGMEA). In view of coating uniformity, at least propylene glycol monomethyl ether acetate The case of using (PGMEA) is particularly preferable.

  In this case, the content ratio (PGMEA / BI) between PGMEA and the blocked isocyanate group-containing compound (BI) is preferably 100 / 0.1 to 10/1, and preferably 100 / 0.5 to 100 / 0.5 in terms of coating uniformity. 20/1 is more preferable.

The amount of the solvent used can be appropriately selected according to the physical properties of the colored polymerizable composition for color filter to be prepared, but the colored polymerizable composition for color filter of the present invention is used for coating by the slit method. Therefore, it is preferable to contain so that solid content may be 20 mass% or less from a viewpoint of application | coating suitability.
Among these, the solid content of the colored polymerizable composition for the color filter is preferably in the range of 5 to 20% by mass in terms of further improving the coating suitability and reducing display unevenness when displaying an image. The range of 17% by mass is more preferable, and it is preferable to contain an amount of a solvent that satisfies this range.

(G) Other additives The colored polymerizable composition for a color filter of the present invention includes, in addition to the above-described components, various additives as necessary, for example, a filler, the (B) carboxyl group-containing binder, and (D). A polymer compound other than the compound having a blocked isocyanate group, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended.

  Specific examples of additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, and hydroxyl group Polymers added with acid anhydrides, alcohol-soluble nylons, alkali-soluble resins such as phenoxy resins formed from bisphenol A and epichlorohydrin; nonionic, kachin and anionic surfactants, specifically Is a phthalocyanine derivative (commercially available product: EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, poly Oxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, the same manufactured by BASF) 701, 704, 901, 904, 150R1, etc.) Nonionic surfactants; anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA- 7, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (Sannopco Polymer dispersing agents such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 27000, 24000, 26000, 28000, etc. (manufactured by Geneca) Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ( Denka Co., Ltd.), and Isonetto S-20 (manufactured by Sanyo Chemical Industries, Ltd.);

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol) , 2, -Antioxidants such as di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone; and sodium polyacrylate And the like.

Further, when the alkali solubility in the non-exposed part (non-cured part) is promoted and the developability is further improved, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less can be added. .
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

In addition to the above-mentioned components, it is preferable to add a thermal polymerization inhibitor to the colored polymerizable composition for color filters of the present invention in order to suppress changes in viscosity over time at room temperature or refrigerated storage. By adding a thermal polymerization inhibitor, the storage stability of the composition can be enhanced.
For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2 ' -Methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful.
The addition amount of the thermal polymerization inhibitor in the colored polymerizable composition for a color filter is usually 100 ppm to 1% by mass, preferably about 500 ppm, with respect to the (C) photopolymerizable compound.

-Preparation method of colored polymerizable composition for color filter-
The colored polymerizable composition for a color filter of the present invention comprises (A) a colorant, (B) a carboxyl group-containing binder, (C) a photopolymerizable compound, (D) a compound having a blocked isocyanate group, and (E) photopolymerization. It can be prepared by mixing an initiator and other additives as required together with the solvent (F) and mixing and dispersing them using a desired mixer and disperser.
The step of mixing and dispersing is preferably composed of kneading and dispersing followed by fine dispersion treatment, but it is also possible to omit the kneading and dispersion and to have only fine dispersion treatment.

<Color filter and manufacturing method thereof>
The color filter of the present invention is produced using the above-described colored polymerizable composition for a color filter of the present invention, and is configured by providing a plurality of colored patterns. Since the colored polymerizable composition for a color filter of the present invention is used, adhesion with the support is good, pattern peeling (lifting) is prevented, and high-quality image display with reduced display unevenness can be performed. .

The color filter of the present invention can be produced by a method appropriately selected from known methods without particular limitation as long as it is a method using the colored polymerizable composition for a color filter of the present invention. Among them, in the present invention, a coating film forming step of forming a colored film by applying the colored polymerizable composition for a color filter of the present invention by a slit method, an exposure step of exposing the coated colored film, and exposure A process of developing the colored film is repeated at least twice and a plurality of color patterns are sequentially formed on the same support to produce a color filter (the color filter of the present invention). It is preferable to use the manufacturing method.
Hereinafter, the manufacturing method of the color filter of the present invention will be described in detail, and details of the color filter of the present invention will be described through the description.

-Coating film formation process-
In the coating film forming step, the colored polymerizable composition for a color filter of the present invention is applied by a slit method to form a colored film. Since the slit coating is performed using the colored polymerizable composition for a color filter of the present invention, coloring is performed when the composition solution is further slit-coated in a form in contact with the existing pattern, such as by overcoating from above the existing pattern. It is possible to prevent pattern lifting and penetration unevenness and development residue during development, and to produce a color filter with good image display characteristics with reduced display unevenness.

According to the slit method, liquid saving is possible, and a film with uniform thickness and high flatness can be formed.
As a coating method by the slit method, it is preferable to perform coating using a slit-like nozzle having a slit-like hole in a portion from which the liquid is discharged, from the viewpoint of displaying an image without display unevenness while maintaining height accuracy. . Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit coaters having slit-like nozzles described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.

  Slit coating has a slit (gap) with a width of several tens of microns at the tip, and a coating head having a length corresponding to the coating width of a rectangular substrate, and a clearance (gap) with the substrate of several tens to several hundreds of microns. The coating liquid supplied from the slit can be applied to the substrate with a predetermined discharge amount by keeping the substrate and the coating head at a constant relative speed.

  In addition, drying (prebaking) of the film | membrane by the coloring polymeric composition for color filters of this invention apply | coated on the support body is 10 to 300 second in the temperature range of 50-140 degreeC using a hotplate, oven, etc. It can be performed under conditions.

-Exposure process-
In the exposure step, the colored film applied and formed in the coating film forming step is exposed.
The exposure is performed by irradiating light through a predetermined mask pattern, and the colored film portion irradiated with light is cured.

  As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used.

-Development process-
In the development step, the colored film exposed in the exposure step is developed.
In this step, the unirradiated portion (uncured portion) of the colored film is developed and removed using a developer, whereby a photocured portion remains and a patterned film is formed. This pattern-like film is a colored pixel that is provided with a plurality of colors (two colors or three or more colors) on the same support and constitutes a color filter.

In development, the uncured part after exposure is eluted in the developer, leaving only the cured part. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Any developer can be used as long as it dissolves the film of the colored polymerizable composition in the uncured part while not dissolving the cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

Examples of the organic solvent include the solvents described above that can be used when preparing the colored polymerizable composition for a color filter of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned.

  In addition, when alkaline aqueous solution is used as a developing solution, generally it wash | cleans (rinse) with water after image development.

After the development, excess developer is washed away, dried, and then generally heated (post-baked) at a temperature of 100 to 240 ° C.
The post-baking is a post-development heating for complete curing, and is usually performed at a temperature of about 200 ° C. to 250 ° C. (hard baking). This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

As the support, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like obtained by attaching a transparent conductive film to these, used for solid-state imaging devices, etc. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate, and a plastic substrate. On these substrates, usually, black stripes for isolating each pixel are formed.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

  In the method for producing a color filter of the present invention, the process group including the coating film formation process, the exposure process, and the development process is repeated at least twice to sequentially form a pattern of two or more colors on the same support. By doing so, a color filter is produced. When the above process group is completed once, and when it is repeated once more or twice (or twice more when producing a color filter of three colors of red, blue, and green), an existing pattern (for example, the first color pattern ( Example: When a colored film (for example, the second color (eg, colored film for forming a blue pixel)) is applied and formed on the pattern forming surface of the support on which the red pixel)) is formed in the coating film forming step, the solvent Is longer than that of spin coating, etc., but it is possible to prevent unevenness due to lifting and soaking from the support of the existing pattern, and to suppress development residue in the next development process, which is finer and more precise. A color filter with excellent adhesion and reduced display unevenness when displaying an image can be obtained.

  The color filter of the present invention comprises, on a support, at least a pixel group composed of two or more colored pixels having different colors formed from a color polymerizable composition for a color filter (and optionally the pixel group). A black matrix that separates the constituent pixels from each other is provided.

  The pixel group may be a pixel group composed of two colored pixels or three color pixels that exhibit different colors, or a pixel group composed of four or more colored pixels that represent different colors. There may be. For example, in the case of being composed of three colors, it is preferably composed of a pixel group composed of colored pixels of three hues of red (R), green (G), and blue (B). When arranging a pixel group composed of three colors of red, green, and blue, a mosaic type, a triangle type, or the like is preferable, and any arrangement may be used when four or more types of pixel groups are disposed.

  In the above description, the application of the pigment dispersion composition and the photocurable composition of the present invention has been described mainly focusing on the use of a color filter. However, the formation of a black matrix that isolates each colored pixel constituting the color filter is also described. Can be applied. The black matrix is subjected to pattern exposure and development using the colored polymerizable composition for a color filter of the present invention using a black pigment such as carbon black or titanium black as a pigment, and then post-baked as necessary to form a film. It can be formed by accelerating the curing of.

<Display device>
The display device of the present invention is configured by providing the above-described color filter of the present invention. The display device of the present invention includes a color filter prepared using the above-described colored polymerizable composition for a color filter, and the colored pattern constituting the color filter adheres to the support without causing lifting. Therefore, high-quality image display with reduced display unevenness can be performed.

  Examples of the display device include display devices such as a liquid crystal display device, a plasma display display device, an EL display device, and a CRT display device. For the definition of display devices and explanation of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Device (written by Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year).

  A liquid crystal display device is preferable as the display device provided with the color filter of the present invention. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Investigative Research Institute, Inc., 1994)”.

  The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”. Especially, it is effective for a color TFT type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention can also be applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC Co., Ltd., 1994)”, “2003 Current Status and Future Prospects for Liquid Crystal Related Markets (Volume 2)” , Fuji Chimera Research Institute, Ltd., published in 2003).

  As applications, it can be applied to applications such as televisions, personal computers, liquid crystal projectors, game machines, mobile terminals such as mobile phones, digital cameras, car navigation systems, and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

(Example 1)
-Preparation of blocked isocyanate 1-
A flask equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen gas injection tube, and a dropping funnel, hexamethylene diisocyanate trimer (Coronate HX, manufactured by Nippon Polyurethane Co., Ltd.) 100 parts, methyl isobutyl ketone 26 parts , And 0.1 parts of dibutyltin dilaurate were weighed and 44 parts of methyl ethyl ketoxime was added dropwise over 1 hour from a dropping funnel while stirring in a nitrogen atmosphere. Thereafter, the liquid temperature was maintained at 70 ° C., and the reaction was continued until the absorption of the NCO group in the reaction liquid disappeared as measured by an infrared spectrometer. Thereafter, methyl isobutyl ketone was added to prepare blocked isocyanate 1 (number of blocked isocyanate groups: 3) having a nonvolatile content of 70%.

-Preparation of black resist-
First, K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 below are weighed out, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then Methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisdiethoxycarbonylmethylamino) -3' in the amounts shown in Table 1 -Bromophenyl] -s-triazine and Surfactant 1 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and 30 at 150 ° C. at a temperature of 40 ° C. (± 2 ° C.). By stirring for a minute, a black (K) resist was obtained.
The amounts listed in Table 1 below are parts by mass and are as follows in detail.

* K pigment dispersion 1
・ Carbon black (Nexex 35, manufactured by Degussa) ... 13.1%
Dispersant 1 (Compound 1 below) ... 0.65%
-Random copolymer of polymer (benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]), molecular weight 37,000) ... 6.72%
・ Propylene glycol monomethyl ether acetate 79.53%

* Binder 2
・ Random copolymer of polymer (benzyl methacrylate / methacrylic acid (= 78/22 [molar ratio]), molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%
* DPHA solution ・ Dipentaerythritol hexaacrylate ・ ・ ・ 76%
(Polymerization inhibitor MEHQ 500ppm, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA)
・ Propylene glycol monomethyl ether acetate: 24%
* Surfactant 1
・ The following structure 1 ... 30%
・ Methyl ethyl ketone 70%

-Preparation of pigment dispersion-
<Pigment dispersion for G (G1)>
C. I. Pigment Green 36 (brominated phthalocyanine green), C.I. I. Pigment Yellow 150, Disperbyk-161 (manufactured by Big Chemie, pigment dispersant), binder 1 (benzyl methacrylate / methacrylic acid / ethoxymethyl acrylate (= 75/15/10 [mass ratio]) copolymer (alkali-soluble resin, weight) A propylene glycol monomethyl ether acetate solution (solid content: 50% by mass)) having an average molecular weight Mw of 10,000) and propylene glycol monomethyl ether acetate (organic solvent) are blended in amounts shown in Table 2 below, and premixing is performed. Thereafter, the mixture was dispersed with a motor mill M-50 (manufactured by Eiger Japan Co., Ltd.) for 9 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm to prepare a pigment dispersion (G1) for G.

<R pigment dispersion (R1)>
In the G pigment dispersion G1, an R pigment dispersion R1 was prepared in the same manner as the G pigment dispersion G1, except that the pigment and other components were changed as shown in Table 2 below.
<Pigment dispersion for B (B1)>
A pigment dispersion B1 for B was prepared in the same manner as the pigment dispersion G1 for G, except that the pigment and other components of the pigment dispersion G1 for G were changed as shown in Table 2 below.

-Preparation of colored resist for pixels-
<Colored resist for G>
In accordance with the formulation shown in Table 3 below, each component of the organic solvent, polymerizable monomer, binder, photopolymerization initiator, and surfactant is mixed and stirred at 25 ° C. for 30 minutes, and then it is confirmed that there is no insoluble matter. As a result, a monomer solution was obtained. Next, with stirring, the obtained monomer liquid and blocked isocyanate 1 (block isocyanate group-containing compound) are slowly added to the G pigment dispersion (G1) obtained above, and stirred at 25 ° C. for 30 minutes. Thus, a colored resist for G (resist G-1) was prepared. The solid content of the resist G-1 was 13.4%.

<G colored resist, B colored resist>
In the same manner as described above, a monomer solution was obtained according to the formulation shown in Table 3 below, and a colored resist for R (resist R-1) and a colored resist for B (resist B-1) were prepared in the same manner.
The solid content of the resist R-1 was 13.2%, and the solid content of the resist B-1 was 14.3%.

-Formation of black (K) image-
An alkali-free glass substrate (hereinafter simply referred to as “glass substrate”) was cleaned with a UV cleaning device, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. Thereafter, the glass substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling this glass substrate and adjusting the temperature to 23 ° C., the black color (K) prepared above with a coater for glass substrate (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. ) A resist was applied. Subsequently, after part of the solvent was dried for 30 seconds with a vacuum drying apparatus VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating layer, it was pre-baked at 120 ° C. for 3 minutes, and a dark color photosensitive film with a thickness of 2 μm. Layer K1 was obtained.

Using a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, the mask surface and dark color photosensitivity with the substrate and mask (quartz exposure mask with image pattern) standing vertically The distance from the layer K1 was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .

  Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the dark photosensitive layer K1, a KOH developer (containing nonionic surfactant, trade name: CDK-1, Fuji Film Electronics Material) The product was manufactured by showering at 23 ° C. for 80 seconds at a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water is sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and ultrapure water is sprayed from both sides with a shower nozzle to adhere the developer and the black matrix layer. The dissolved matter was removed, and the liquid was drained with an air knife to obtain a black (K) pattern. Thereafter, heat treatment was performed at 220 ° C. for 30 minutes to form a black (K) image.

-Formation of red (R) pixels-
The resist R-1 prepared above is applied to the K image forming surface of the glass substrate on which the black (K) image is formed in the same manner as the formation of the K image, and exposure and development are performed to obtain a patterning image. Further, heat treatment or the like was performed to form a heat-treated R pixel. The film thickness of this heat-treated R pixel was 2.1 μm.

-Evaluation 1
1. Development residue On the glass substrate on which the resist R-1 is applied and development is completed, ethanol is dropped on the glass surface on which the K image is formed and the K image is not formed, and the glass surface is covered with a dust-free cloth. Rubbed 10 times. Then, the presence or absence of the resist residue was confirmed by visually observing the presence or absence of the resist color adhering to the dust-free cloth.
At this time, the case where no resist color was observed was evaluated as “no residue”, and the case where a resist color was observed was evaluated as “with residue”. The evaluation results are shown in Table 5 below.

-Formation of green (G) pixels-
A heat-treated G pixel was formed in the same manner as the R pixel formation using the resist G-1 prepared above on the K image etc. formation surface side of the glass substrate on which the K image and the R pixel were formed. The film thickness of this heat-treated G pixel was 2.1 μm.
Further, the presence or absence of a resist residue after the formation of the G pixel was confirmed by the same method as the evaluation of the development residue after the formation of the R pixel.

-Formation of blue (B) pixels-
Using the resist B-1 prepared above on the glass image forming surface side of the glass substrate on which the K image, R pixel, and G pixel are formed, the heat-treated B pixel in the same manner as the formation of the R pixel. Formed. The film thickness of this heat-treated B pixel was 2.1 μm.
Furthermore, the presence or absence of a resist residue after forming the B pixel was confirmed by the same method as the evaluation of the development residue after forming the R pixel.

  As described above, a color filter substrate on which color filters composed of three colors RGB were formed.

-Evaluation 2-
The following evaluation was performed on a glass substrate (color filter substrate) on which each pixel of red (R), green (G), and blue (B) was formed. The evaluation results are shown in Table 5 below.

2. Evaluation of Adhesion of Pixels R pixels, G pixels, and B pixels formed on a glass substrate were cut vertically and horizontally with a cutter at intervals of 5 mm. In addition, the cut part was made into 25 mm square. Next, the cut portion was immersed in PGMAC (propylene glycol monomethyl ether acetate) for 15 minutes and then dried at room temperature for 30 minutes. Thereafter, an adhesive tape (Nichiban cellophane tape) was attached to the cut surface of the pixel, the tape was peeled off, and the presence or absence of pixel peeling was examined.
Here, the case where pixel peeling was not observed was evaluated as “◯”, and the case where pixel peeling was observed was evaluated as “x”.

3. Unevenness evaluation of R, G, B pixels Each of the R pixel, G pixel, and B pixel formed on the glass substrate was observed using an optical microscope, and the presence or absence of color unevenness in each pixel was evaluated.
Here, the case where no color unevenness was observed was evaluated as “◯”, and the case where color unevenness was observed in any of R, G, B pixels was evaluated as “X”.

-Liquid crystal display device-
A transparent electrode made of an ITO (Indium Tin Oxide) film was further formed on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above by sputtering.

Next, a spacer was formed in a portion corresponding to the upper part of the black matrix on the formed ITO film by the same method as in Example 1 of JP-A-2006-64921.
Separately, a glass substrate was prepared as a counter substrate.
Then, patterning was performed for the PVA mode on the ITO film and the counter substrate of the color filter substrate, respectively, and an alignment film made of polyimide was further provided thereon.

  After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided around the pixel group constituting the color filter, and a liquid crystal for PVA mode is dropped to face. After being bonded to the substrate, the bonded glass substrate was irradiated with UV, and then heat-treated to cure the sealant to obtain a liquid crystal cell. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, FR1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a green (G) LED, and DB1112H (as a blue (B) LED. A side-light type backlight is constructed using a chip-type LED manufactured by Stanley Electric Co., Ltd., which is placed on the opposite side (rear side) of the liquid crystal cell to which the polarizing plate is attached. The device.

-Evaluation 3-
4). Display unevenness A gray test signal was input to the liquid crystal display device, and the presence or absence of unevenness when a gray image was displayed was observed visually and with a magnifying glass, and judged according to the following evaluation criteria.
A: Unevenness was hardly observed.
Δ: Some unevenness was observed, but was within an acceptable range for practical use.
X: Unevenness was remarkably confirmed.

(Example 2)
-Preparation of blocked isocyanate 2-
Adduct body of hexamethylene diisocyanate and 1,3-butanediol (C-2612 manufactured by Nippon Polyurethane Industry Co., Ltd.) to a flask equipped with a thermometer, stirring device, reflux cooling device, nitrogen gas injection tube and dropping funnel. 100 parts, 26 parts of methyl isobutyl ketone, 47 parts of ε-caprolactam, and 0.1 part of dibutyltin dilaurate are weighed and maintained at 100 ° C. with stirring under a nitrogen atmosphere. The reaction was continued until the absorption of NCO groups disappeared. Thereafter, methyl isobutyl ketone was added to prepare blocked isocyanate 2 (number of blocked isocyanate groups: 2) having a nonvolatile content of 70%.

A colored resist for G (resist G-2) and a colored resist for R (resist R) in the same manner as in Example 1 except that the blocked isocyanate 1 was replaced with the blocked isocyanate 2 obtained above in Example 1. -2) and a colored resist for B (resist B-2) were prepared, a color filter and a liquid crystal display device were produced, and the same evaluation was performed.
The solid contents of the resists G-2, R-2, and B-2 are the same as those in Example 1.

(Example 3)
In the preparation of the colored resist for pixel in Example 1, the same manner as in Table 3 except that the formulation shown in Table 3 was changed to the formulation shown in Table 4 below, and a colored resist for G (resist G-3) and a colored resist for R (Resist R-3) and a colored resist for B (resist B-3) were prepared. The solid content of the resist G-3 was 20.8%, the solid content of the resist R-3 was 20.9%, and the solid content of the resist B-3 was 21.0%. It was. Then, the color filter and the liquid crystal display device were prepared in the same manner as in Example 1 except that the resists R-1, G-1, and B-1 were replaced with the resists R-3, G-3, and B-3, respectively. The same evaluation was performed while producing.

(Comparative Example 1)
In Example 1, G colored resist (resist G-4), R colored resist (resist R-4) were the same as in Example 1 except that the blocked isocyanate 1 listed in Table 3 was not added. And a colored resist for B (resist B-4) were prepared, and a color filter and a liquid crystal display device were produced, and the same evaluation was performed.

(Comparative Example 2)
In Example 1, instead of adding 2 parts of blocked isocyanate 1, G was added in the same manner as in Example 1 except that 1.4 parts of unblocked isocyanate (hexamethylene diisocyanate trimer) was added. Color resist (resist G-5), color resist for R (resist R-5), and color resist for B (resist B-5) are prepared, and a color filter and a liquid crystal display device are produced, and the same evaluation is performed. Was done.

  As shown in Table 5, the color filters of the examples had better pixel adhesion and fewer development residues than the color filters of the comparative examples. Further, the color unevenness of each pixel of the color filter and the display quality when displaying an image as a liquid crystal display device were also excellent. Example 3 was slightly better than the comparative example, although display unevenness was slightly observed as compared with Examples 1-2.

Claims (6)

  (A) a colorant, (B) a carboxyl group-containing binder, (C) a photopolymerizable compound, (D) a compound having a blocked isocyanate group, (E) a photopolymerization initiator, and (F) a solvent, A colored polymerizable composition for a color filter used for coating by a slit method.   The colored polymerizable composition for a color filter according to claim 1, wherein the compound (D) having a blocked isocyanate group has two or more blocked isocyanate groups.   The colored polymerizable composition for a color filter according to claim 1 or 2, wherein at least one of the (F) solvent is propylene glycol monomethyl ether acetate, and the solid content is 5 to 20% by mass. .   The color filter produced by forming a coloring pattern using the coloring polymeric composition for color filters of any one of Claims 1-3.   A coating film forming step of forming a colored film by applying the colored polymerizable composition for a color filter according to any one of claims 1 to 3 on a support by a slit method, and the color formed by coating Manufacturing of a color filter in which a process group including an exposure process for exposing a film and a development process for developing the exposed colored film is repeated at least twice, and a plurality of colored patterns are sequentially formed on the same support. Method.   A display device comprising the color filter according to claim 4 or a color filter produced by the method for producing a color filter according to claim 5.