JP4667989B2 - Photocurable composition, color filter and method for producing the same - Google Patents

Description

  The present invention relates to a photocurable composition suitable for forming a colored image constituting a color filter used in a liquid crystal display element (LCD), a solid-state image sensor (CCD, CMOS, etc.), and the like. The present invention relates to a used color filter and a method for manufacturing the same.

  As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. It has the advantage of being stable to heat and the like. Further, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate by a spin coater or a roll coater and dried to form a coating film, and the coating film is subjected to pattern exposure and development. Colored pixels are formed, and a color filter can be obtained by repeating this operation for each color.

  Examples of the pigment dispersion method include a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin (see, for example, Patent Documents 1 to 4).

  In recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution in the conventional pigment dispersion system, and there is a problem that color unevenness occurs due to the coarse particles of the pigment. For this reason, it was not suitable for uses requiring a fine pattern such as a solid-state imaging device.

  In order to solve such a problem, a technique of using a dye instead of a pigment has been conventionally proposed (for example, see Patent Document 5). However, in general, a curable composition containing a dye is inferior to a curable composition using a pigment in terms of various properties such as light resistance, heat resistance, solubility, and coating uniformity. there were.

  In particular, color filters for solid-state imaging devices (image sensors) tend to be thinned to a thickness of 1.5 μm or less in order to cope with improved shading and device miniaturization. However, when such a thin film is formed, the content of the colorant contained in the film is inevitably lowered, which causes a problem in terms of color characteristics (color value). Such a tendency is particularly remarkable when a dye is used rather than when a pigment is used as a colorant.

  That is, when an organic pigment is used, the molecules that form a chromophore are present in an aggregated state in the color filter, whereas when a dye is used, the molecules are dispersed in a molecular state. In addition to the chromophore molecules, molecular chains that improve their properties are bound to increase durability and light resistance, so the molecular chains that become chromophores are further diluted. , The color value will decrease by that much.

  As described above, in order to meet the demand for thinning the color filter in the solid-state imaging device, it is necessary to increase the content ratio of the colorant in the color filter. This requirement is particularly important when dyes are used rather than when pigments are used as colorants.

  However, increasing the content ratio of the colorant inevitably decreases the ratio of other components contained in the composition. In this case, as a matter of course, when the ratio of the other components is lowered, the photocurability and the alkali developability are lowered, so that there is a limit to the improvement of the content ratio of the colorant. In particular, when a dye is used as a colorant, the chromaticity is significantly reduced as the film is made thinner than when a pigment is used, and it is very difficult to achieve a balance with practical characteristics other than chromaticity.

JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375

  An object of the present invention is to provide a photocurable composition that uses a dye, has a sufficient color value, sensitivity, and curability, and is excellent in pattern rectangularity and developability. Another object of the present invention is to provide a color filter having a sufficient color value and excellent pattern rectangularity, and a method for producing the same.

Specific means for solving the above problems are as follows.
<1> A photocurable composition containing at least a dye, a photopolymerizable compound, and a photopolymerization initiator, wherein the content of the dye is 40% by mass or more based on the total solid content. And the total content of the said dye, the said photopolymerizable compound, and the said photoinitiator is 90 mass% or more with respect to the total solid, It is a photocurable composition characterized by the above-mentioned.

In the photocurable composition of the present invention, 60 % by mass or more of the dye is an acid dye.

< 2 > A pixel is provided on a support, and the pixel is obtained by patterning a coating film formed using the photocurable composition of <1 > by a photolithography method using alkali development. It is a color filter characterized by this.

< 3 > In the wavelength range of 400 nm to 700 nm, the minimum transmittance is 10% or less, and the difference between the maximum transmittance and the minimum transmittance in the wavelength range is 75% or more. 2 > color filter.

< 4 > The color filter according to < 2 > or < 3 >, wherein the pixel has a thickness of 1.5 μm or less.

< 5 > The color filter according to <2> to < 4 >, wherein a length of a maximum side of the pixel is 5.0 μm or less.

< 6 > A coating film is formed on the support using the photocurable composition of <1 >, and the coating film is patterned by a photolithography method using alkali development to form pixels. It is a manufacturing method of a color filter.

  An object of the present invention is to provide a photocurable composition that uses a dye, has a sufficient color value, sensitivity, and curability, and is excellent in pattern rectangularity and developability. In addition, the present invention can provide a color filter having a sufficient color value and excellent pattern rectangularity, and a method for producing the same.

  Hereinafter, the photocurable composition of the present invention, a color filter formed using the photocurable composition, and a production method thereof will be described in detail.

<< Photocurable composition >>
The photocurable composition of the present invention is a photocurable composition containing at least a dye, a photopolymerizable compound, and a photopolymerization initiator, wherein the content of the dye is based on the total solid content. 40% by mass or more, and the total content of the dye, the photopolymerizable compound and the photopolymerization initiator is 90% by mass or more based on the total solid content. And an alkali-soluble resin and an organic solvent.
In the photocurable composition of the present invention, the content of the dye is 40% by mass or more based on the total solid content, and the total content of the dye, the photopolymerizable compound, and the photopolymerization initiator is Since the alkali-soluble resin is not substantially used since it is 90% by mass or more based on the total solid content, the curability is high even if the content of the dye is as large as 40% by mass based on the total solid content. The content of the photopolymerizable compound and the photopolymerization initiator, which are components, can be maintained. As a result, practical characteristics (color value, sensitivity, curability, etc.) of the color filter as a coating film are ensured, and the color value and pattern profile (pattern rectangularity) of the pixel of the obtained color filter are improved. be able to.

  As above-mentioned, the total content of dye, a photopolymerizable compound, and a photoinitiator in the photocurable composition of this invention is 90 mass% or more with respect to the total solid. In other words, the total content of solid components other than the dye, the photopolymerizable compound and the photopolymerization initiator in the photocurable composition of the present invention is less than 10% by mass. When the total content of the dye, the photopolymerizable compound and the photopolymerization initiator is less than 90% by mass with respect to the total solid content, the color value, sensitivity, curability and the like cannot be sufficiently improved. The total content of the photopolymerizable compound and the photopolymerization initiator is preferably 93% by mass or more, more preferably 95% by mass or more based on the total solid content.

Moreover, the photocurable composition of this invention makes an acid dye 60 mass% or more with respect to all the dyes. Thereby, alkali developability can be maintained and the rectangularity and developability of the pattern obtained can be made favorable.
Hereinafter, each component contained in the photocurable composition of the present invention will be described.

(dye)
As the dye in the present invention, an organic solvent-soluble dye or the like can be used without particular limitation, and examples thereof include conventionally known dyes for color filters. Examples of the known dyes include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP-T-2592207, US Patent. No. 4,808,501, U.S. Pat.No. 5,667,920, U.S. Pat.No. 5,059,500, JP-A-5-333207, JP-A-6-35183, Examples thereof include dyes described in JP-A-6-51115 and JP-A-6-194828. From the viewpoint of chemical structure, triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, etc. can be mentioned. . Particularly preferable dyes in the present invention include pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes, and anthrapyridone dyes.

  In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be preferably used as the dye in the present invention from the viewpoint of completely removing the binder and / or dye by development. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof may be suitably used as the dye in the present invention. it can.

(Acid dyes)
In the photocurable composition of the present invention, from the viewpoint of improving the rectangularity of the pattern, 35% by mass or more of the total dye is preferably an acid dye, and more preferably 45% by mass or more is an acid dye. 60% by mass or more is particularly preferably an acid dye.
The acid dye will be described. The acidic dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid, phenolic hydroxyl group, etc., but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, curability. It is selected in consideration of all required performance such as interaction with other components in the composition, light resistance, heat resistance and the like.

Hereinafter, specific examples of the acid dye will be given. However, the acidic dye in the present invention is not limited to these. For example,
Acid Black 24;
Acid Blue 1,7,9,15,83,86,90,103,108,113,120,249,
Acid Green 1, 3, 5, 9, 16, 50;
Acid Orange 7, 8, 10, 12, 50, 51, 52, 63;

Acid Red 4, 8, 14, 17, 18, 26, 27, 51, 66, 73, 80, 87, 88, 91, 92, 94, 103, 111, 114, 145, 150, 151;
Acid Violet 9, 17, 49;
Acid Yellow 1,7,9,11,17,23,34,36,38,40,65,72,76,135,228;

Direct Yellow 34;
Direct Orange 41, 61, 70;
Direct Violet 54;
Direct Blue 86, 108, 109, 199;
Modern Yellow 8, 10, 20;
Modern Red 9, 32;
Modern Violet 2,41;
Modern Blue 1,3;
Modern Green 4;
Food Yellow 3;

Valentine Blue 2620
And derivatives of these dyes.

  As the derivative of the acid dye, an inorganic salt of an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or the like can be used, and a curable composition It is not particularly limited as long as it can be dissolved as a solution, but it needs solubility, absorbance, interaction with other components in the curable composition, light resistance, heat resistance, etc. in an organic solvent or developer. It is selected in consideration of all the performance to be performed.

  The salt of the acidic dye and the nitrogen-containing compound will be described. The method of forming a salt of an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.

The nitrogen-containing compound that forms a salt with the acid dye and the nitrogen-containing compound that forms an amide bond with the acid dye will be described.
Nitrogen-containing compounds are the solubility of salts or amide compounds in organic solvents and developers, salt-forming properties, dye absorbance / color value, interaction with other components in the curable composition, and heat resistance as a colorant. In addition, it is selected in consideration of all of light resistance and the like. When selecting only in terms of absorbance and color value, the nitrogen-containing compound is preferably as low as possible in molecular weight, more preferably having a molecular weight of 300 or less, more preferably having a molecular weight of 280 or less, and a molecular weight of 250 or less. Those are particularly preferred.

  The molar ratio (hereinafter referred to as “n”) of the nitrogen-containing compound / acid dye in the salt of the acid dye and the nitrogen-containing compound will be described. Said n is a value which determines the molar ratio of an acidic dye molecule and the amine compound which is a counter ion, and can be freely selected according to the salt forming conditions of the acidic dye-amine compound. Specifically, a number between 0 <n ≦ 5 of the number of functional groups of the acid in the acid dye is practically used, and the solubility in organic solvents and developers, salt formation, absorbance, and curable composition It is selected in consideration of all necessary performance such as interaction with other components, light resistance, heat resistance and the like. When selecting from the standpoint of absorbance only, n is preferably a value between 0 <n ≦ 4.5, more preferably a value between 0 <n ≦ 4, and 0 <n. It is particularly preferable to take a numerical value between ≦ 3.5.

Since the acidic dye shown above is an acidic dye due to the introduction of an acidic group in its structure, it can be made a non-acidic dye by changing its substituent.
In some cases, the acid dye works favorably during alkali development, but on the other hand, it may become over-developed, and a non-acid dye may be preferably used.
These dyes use single-color dyes when forming the complementary colors of yellow, magenta, and cyan, respectively. When forming the primary colors of red, green, and blue, two or more dyes are combined. Is used. In the present invention, it is preferable to assemble a primary color system by combining two or more kinds of dyes.

  In the photocurable composition of the present invention, the content of the dye in all solid components is 40% by mass or more. When the content of the dye is less than 40% by mass, a sufficient color density cannot be obtained when the film thickness of the pixel is 1.5 μm or less. For example, the color separation of an image sensor using the color density can be reduced. It will decrease. The content of the dye is preferably 45% by mass or more, and more preferably 50% by mass with respect to the total solid content. The upper limit of the content of the dye is not particularly limited, but is 80% by mass or less from the viewpoint of securing a certain amount of the photopolymerizable compound and the photopolymerization initiator in order to prevent the curability and sensitivity from being lowered. It is preferable that it is 70 mass% or less.

(Photopolymerizable compound)
Next, the photopolymerizable compound will be described. Examples of the photopolymerizable compound include radical polymerizable monomers. The photopolymerizable compound used in the present invention is preferably a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure.

  Examples of the radical polymerizable monomer 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 , Trimethylolethane 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 (meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then (meth) acrylated after addition of ethylene oxide or propylene oxide; 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, Polyester acrylates described in JP-B Nos. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof; Can be mentionedFurthermore, the Japan Adhesion Association Vol. No. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers.

  The content of the photocurable compound in the photocurable composition of the present invention is determined so that the total content of the dye and the photopolymerization initiator is 90% by mass or more as described above. From the viewpoint of concentration and the like, 93% by mass or more is preferable with respect to the total solid content, and 95% by mass or more is particularly preferable.

(Photopolymerization initiator)
Next, the photopolymerization initiator will be described. A photoinitiator is contained with the above-mentioned photocurable compound in the photocurable composition of this invention. The photopolymerization initiator in the present invention is not particularly limited as long as it can polymerize the photocurable compound, but is preferably selected from the viewpoints of properties, initiation efficiency, absorption wavelength, availability, cost, and the like. .

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone. Examples thereof include compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

  Examples of the active halogen compound that is the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl, and the like. -5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxy) Styryl) -1,3,4-oxadiazole, and the like.

  Examples of the active halogen compound which is a halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho-) described in JP-A-53-133428. 1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specific examples of the halomethyl-s-triazine compound include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3 , 4-methylenedioxyphenyl) -1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphtho) -1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-tria 2- (4-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine,

2- [4- (2-Ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5- Methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(5-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- 6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s -Triazine,

4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, -Di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine ,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine,

4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick Romechiru) -s- triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine,

4- (o-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloro) Ethylamino) -2,6-di (trichloromethyl) -s-triazine.

  In addition, as the photopolymerization initiator, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, manufactured by Midori Chemical Co., Ltd., TAZ-123), T series (for example, T-OMS, T-BMP, TR, TB) manufactured by PANCHIM, Irgacure series (for example, Irgacure 651, Irgacure 184) manufactured by Ciba Specialty Chemicals , Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [ 4- (Phenylthio) phenyl -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 2-benzyl-2-dimethyl Amino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone,

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2, 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like are also useful.
Among these photopolymerization initiators, oxime compounds are preferable. For example, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (O— Acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is particularly preferred.

These photopolymerization initiators can be used in combination with a sensitizer and a light stabilizer.
Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- ( Dimethylamino) phenyl-p-methyls Rilketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, etc. Can be mentioned.

In addition to the above-described photopolymerization initiator, other known photopolymerization initiators can be used in the photocurable composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenylketone combination, benzothiazole compound / trimethyl disclosed in Japanese Patent Publication No. 51-48516 And halomethyl-s-triazine compounds.
Further, as described above, the content of the photopolymerization initiator is determined so that the total content combined with the dye and the photopolymerizable compound is 90% by mass or more, but with respect to the photopolymerizable compound. 0.01 to 50 mass% is preferable, 1 to 30 mass% is more preferable, and 1 to 20 mass% is particularly preferable. When the content of the photopolymerizable compound is in the range of 0.01 to 50% by mass, it is possible to prevent the polymerization from proceeding with difficulty, and further to prevent the molecular weight from being lowered and the film strength from being weakened. it can.

(Other additives)
In the photocurable composition of the present invention, an additive can be contained in addition to the above-mentioned dye, photopolymerizable compound and photopolymerization initiator. However, the total content of solid components other than the dye, the photopolymerizable compound and the photopolymerization initiator is less than 10% by mass, preferably less than 7% by mass, based on the total solid content of the composition. More preferably, it is less than 5 mass%.
Hereinafter, additives other than the dye, photopolymerizable compound and photopolymerization initiator that can be used in the photocurable composition of the present invention will be described.

-Alkali-soluble binder-
First, the alkali-soluble binder will be described. The alkali-soluble binder is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Similarly, acidic cellulose derivatives having a carboxylic acid in the side chain are useful.

In addition to the above, the alkali-soluble binder includes a polymer having a hydroxyl group and an acid anhydride added thereto, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful.
The linear organic polymer may be a copolymer of hydrophilic monomers, and examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meta ) Acrylate, (meth) acrylamide, N-methylolacrylamide, secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyl Triazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, or phenoxyhydroxypropyl Meth) acrylate.

-Crosslinking agent-
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent usable in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from Substituted phenolic compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. Divalent glycidyl group-containing low molecular weight compounds such as hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline, trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the (b) melamine compound, guanamine compound, glycoluril compound and urea compound are collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) according to (b).

  The methylol group-containing compound according to (b) can be obtained by heating the alkoxymethyl group-containing compound according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound according to (b) can be obtained by mixing and stirring the methylol group-containing compound according to (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound according to (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds obtained by acylating 1 to 3 or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds according to (b) may be used alone or in combination.

  The crosslinking agent (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. Further, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound according to the above (c) uses a compound in which the phenolic OH group has a hydrogen atom at the 2nd or 4th position as a raw material, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide. It can be obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in the crosslinking agent (c) include phenolic compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol- Compounds obtained by methoxymethylating one or two methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, Compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4 ′ − Suhydroxybiphenyl, TrisP-PA hexamethylol, TrisP-PA hexamethoxymethyl, TrisP-PA hexamethylol compound in which 1 to 5 methylol groups are methoxymethylated, Bishydroxymethylnaphthalenediol, etc. Is mentioned.

  In addition, examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include, for example, a part of the methylol group of the methylol group-containing compound or Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

  The total content of the crosslinking agent in the photocurable composition varies depending on the material, but from the viewpoint of improving curability, 0.1 to 7 with respect to the solid content (mass) of the photocurable composition. % By mass is preferable, 0.1 to 6% by mass is more preferable, and 0.15 to 5% by mass is most preferable.

-Thermal polymerization inhibitor-
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the photocurable composition of the present invention. 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.

-Organic solvent-
The organic solvent that can be used in the present invention is basically not particularly limited as long as the solubility of each component and the coating property of the photocurable composition are satisfied, but in particular, the solubility, coating property, and safety of the dye and binder. Is preferably selected in consideration of Moreover, when preparing the photocurable composition of this invention, it is preferable that at least 2 type of organic solvent is included.

  Examples of the organic 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, alkyl esters, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

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, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

  As described above, these organic solvents may be used in combination of two or more from the viewpoints of solubility of the dye and the alkali-soluble binder, improvement of the coated surface, and the like. In particular, the above-mentioned methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl A mixed solution composed of two or more selected from ether acetate is preferably used.

  The amount of the organic solvent used in the present invention is preferably such that the total solid concentration of the photocurable composition of the present invention is 5 to 80% by mass from the viewpoint of applicability, and 5 to 60% by mass. More preferably, 10-50 mass% is especially preferable.

-Various additives-
The photocurable composition of the present invention further contains various additives such as fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like. be able to.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

Further, when the alkali solubility of the non-image area is promoted and the developability of the photocurable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a low molecular weight of 1000 or less. An organic carboxylic acid 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.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described photocurable composition of the present invention is used.
The color filter of the present invention has a pixel on a support, and the pixel is formed by patterning a coating film formed using the photocurable composition of the present invention by a photolithographic method using alkali development. It is characterized by being obtained. For this reason, the color filter of the present invention has a high color density and is excellent in a rectangular pattern.

The color filter of the present invention preferably has a minimum transmittance of 10% or less in a wavelength range of 400 nm to 700 nm, and a difference between the maximum transmittance and the minimum transmittance in the wavelength range of 75% or more. . Among these, the minimum transmittance is preferably 8% or less, and particularly preferably 6% or less, from the viewpoint of color separation property and transmittance of the color filter. The difference between the maximum transmittance and the minimum transmittance in the wavelength range is preferably 78% or more, and particularly preferably 80% or more. Among these combinations, a more preferable combination is more preferable.
In the color filter of the present invention, the thickness of the pixel formed on the support is preferably 1.5 μm or less, more preferably 1.3 μm or less, from the viewpoint of thinning the color filter. Particularly preferred is 2 μm.
Further, the length of the maximum side of the pixel (the maximum side when the pixel is observed from above) is preferably 5.0 μm or less from the viewpoint of realizing high resolution by increasing the pixel density. More preferably, it is more preferably 3 μm or less.

The color filter manufacturing method of the present invention comprises forming a coating film on a support using the photocurable composition of the present invention, and patterning the coating film by a photolithographic method using alkali development to form pixels. It is characterized by forming.
Specifically, first, the photocurable composition of the present invention is applied onto a support by a coating method such as spin coating, cast coating, roll coating, and the like to form a coating layer (photocurable composition layer). The negative coloring pattern (pixel) can be formed by exposing the layer through a predetermined mask pattern and performing alkali development with a developer such as an alkaline aqueous solution (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.

  Further, in the production of the color filter of the present invention, a color filter having a desired hue can be produced by repeating the image forming step (and the curing step if necessary) for the desired number of hues. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

Examples of the support include soda glass, Pyrex (registered trademark) glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, and photoelectric conversion element substrates used for imaging elements and the like. Examples thereof include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
In addition, an undercoat layer may be provided on these supports, if necessary, for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.

  As the developer, any developer can be used as long as it has a composition that dissolves the uncured portion of the photocurable composition of the present invention and does not dissolve the irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned organic solvent used when preparing the photocurable composition of this invention is mentioned.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  The color filter of the present invention can be used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  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” is based on mass.

[Example 1]
1) Preparation of planarization layer A resist solution, CT-2000L (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied onto a silicon wafer substrate using a spin coater, and then heated and dried in an oven at 220 ° C. for 1 hour. Thus, a planarization layer having a thickness of 2 μm was obtained.

2) Preparation of photocurable composition The components shown below were mixed and dissolved to prepare a blue photocurable composition as the resist layer coating solution.
Solvent: Cyclohexanone 800 parts Photopolymerizable compound: TO-1382 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 78 parts Photopolymerization initiator: o-acyloxime compound (CGI-124: Ciba Specialty Chemicals Co., Ltd.) 34 parts acid dye: Varifast Blue 2620 (manufactured by Orient Chemical Co., Ltd.)
88 parts dye: C.I. I. Solvent Blue MC-3126 (Fuji Photo Film Co., Ltd.) 0 parts

3) Formation of resist layer and exposure / development The above-mentioned photocurable composition is applied onto the planarized layer obtained in 2), and heat-treated (prebaked) at 100 ° C. for 120 seconds with a hot plate to obtain a film thickness. A resist layer was obtained so as to be 1 μm. Next, using an I-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), the resist layer was irradiated with an exposure dose of 3000 mJ / cm ² through a 2 μm Island pattern mask at a wavelength of 365 nm. After exposure, a substrate having a photocurable coating film formed thereon is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type (manufactured by Chemtronics)), and a developer CD-2000 (FUJIFILM Electronics Material) The product was then subjected to paddle development for 60 seconds at 23 ° C. Next, the silicon wafer substrate was fixed to a horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate was rotated at 50 rpm by a rotating device. Meanwhile, pure water was supplied from the jet nozzle in the form of a shower from above the rotation center, rinsed, and then spray-dried to obtain a color filter.

4) Evaluation method For each of the obtained color filters, one pattern was observed from directly above using SEM (S-9260A, manufactured by Hitachi, Ltd.). Are evaluated as “△”, those with a blurred and unclear outline are evaluated as “X”, those with no residue in the unexposed area are “◯”, those with a little residue are “△”, and residues Those with left are evaluated as “×”.

5) Evaluation method of absorption maximum transmittance and absorption minimum transmittance A photocurable composition is applied on a glass substrate, and is heat-treated (prebaked) at 100 ° C. for 120 seconds with a hot plate, so that the film thickness becomes 1.0 μm. Thus, a resist layer was obtained. The resist layer was measured for transmittance at a wavelength of 400 nm to 700 nm using a spectrophotometer (MCPD-2000 manufactured by Otsuka Electronics Co., Ltd.).

[Examples 2 to 4]
In Example 1, except that each composition contained in the photocurable composition was changed to the composition shown in Table 1 below, a photocurable composition was prepared in the same manner as in Example 1, and the color filter was made of silicon. Formed on the wafer. A planarization layer and a resist layer were prepared and evaluated in the same manner as in Example 1.

[Comparative Examples 1-3]
In Example 1, except that each composition contained in the photocurable composition was changed to the composition shown in Table 1 below, a photocurable composition was prepared in the same manner as in Example 1, and the color filter was made of silicon. Formed on the wafer. A planarization layer and a resist layer were prepared and evaluated in the same manner as in Example 1.

Photopolymerizable compound A: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerizable compound B: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Acid dye A: Valifast Blue 2620 (manufactured by Orient Chemical Co., Ltd.)
Dye B: CISolvent Blue MC-3126 (Fuji Photo Film Co., Ltd.)
Resin A: benzyl methacrylate / methacrylic acid copolymer (70/30 copolymerization ratio: average molecular weight 30,000)
-Content A: [(total content of photopolymerizable compound + dye + photopolymerization initiator) / total solid content] × 100 (mass%)
Content rate B: [(total content of dye) / total solid content] × 100 (mass%)
Content C: [(content of acid dye A) / (total content of acid dye A + dye B)] × 100 (mass%)

  As shown in Table 1, in Examples 1 to 4, pixels having a high pattern density with a rectangular pattern profile and no residue were obtained. On the other hand, in the color filters of Comparative Examples 1 to 3, the pixel pattern profile has a tail in Comparative Example 1 and Comparative Example 2, and does not have a rectangular shape, but has a tail toward the adjacent pixels. And apt. In Comparative Example 3, a sufficient color density was not obtained.

Claims (6)

A photocurable composition comprising at least a dye, a photopolymerizable compound, and a photopolymerization initiator, wherein the content of the dye is 40% by mass or more based on the total solid content; and The total content of the dye, the photopolymerizable compound and the photopolymerization initiator is 90% by mass or more based on the total solid content,
60 % by mass or more of the dye is an acid dye, and the photocurable composition.   It has a pixel on a support body, The said pixel is obtained by patterning the coating film formed using the photocurable composition of Claim 1 by the photolitho method using alkali image development. Characteristic color filter.   The minimum transmittance is 10% or less in a wavelength range of 400 nm to 700 nm, and a difference between the maximum transmittance and the minimum transmittance in the wavelength range is 75% or more. Color filter. The color filter according to claim 2, wherein a thickness of the pixel is 1.5 μm or less.   5. The color filter according to claim 2, wherein a length of a maximum side of the pixel is 5.0 μm or less.   A color filter comprising: forming a coating film on the support using the photocurable composition according to claim 1; and patterning the coating film by a photolithography method using alkali development to form a pixel. Manufacturing method.