JP2005134455A - Photosetting composition, and color filter and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosetting composition which can be suitably used for a color filter requiring formation of a fine pattern such as a color filter for an image sensor and which has excellent storage stability, and to provide a color filter and its manufacturing method by using the composition. <P>SOLUTION: The photosetting composition contains at least an alkali-soluble resin, dye, polymerizable monomer, photopolymerization initiator, and solvent, and contains at least either an amide-base organic solvent or water by 3 to 30 mass% with respect to the total mass of the structural components. The color filter and its manufacturing method by using the composition are also presented. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photocurable composition suitable for forming a color filter (in particular, a color filter having a fine colored image used for an image sensor (CCD, CMOS, etc.)), a color filter using the same, and a color filter thereof It relates to a manufacturing method.

  As a method for producing a color filter used for a liquid crystal display element or an image sensor, 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. In such a method, since the pigment is used, the obtained coating film is stable to light, heat and the like. The pigment dispersion method is widely used because patterning is performed by a photolithography method, which has high positional accuracy and is suitable for producing a color filter for a large screen and a high-definition color display.

  To produce a color filter by the pigment dispersion method, first, a radiation-sensitive composition is applied and dried on a glass substrate with a spin coater or roll coater to form a coating film, and the coating film is subjected to pattern exposure and development. To do. Next, in order to improve the solvent resistance, development resistance, and heat resistance of the obtained pattern, a heat treatment (post-bake) step is performed to accelerate the curing of the coating film, thereby producing a highly durable permanent coating film. It has gained. By passing through such a process, the process after the 2nd color can be performed stably, and a color filter can be obtained by repeating this operation for each color.

  However, in the conventional pigment dispersion system, the particle size of the pigment is large, and the resolution is not improved because it scatters ultraviolet rays at the time of exposure, so it has been difficult to meet the demand for higher definition. In addition, since there is a distribution in the particle diameter of the pigment, it is difficult to form uniform pixels without color unevenness, and there is a limit to the use in applications that require a fine pattern such as an image sensor.

  In order to solve the above-described problem, an example in which a color distribution in a pixel is uniformed using a dye has been conventionally known (for example, see Patent Document 1). As described above, in a method using a dye, a dyeing method has been mainly used in the case of a color filter for an image sensor. However, since the dyeing method is a method of forming a pattern using a photosensitive composition on a substrate and dyeing this pattern later, it is difficult to control the degree of dyeing compared to other methods, There were problems such as complicated processes. Therefore, a color filter in which a dye is dissolved in a photosensitive composition, which has solved the disadvantages of the dyeing method and the pigment dispersion method, has been studied.

  One of the important issues when forming a color filter using a dye is to improve the heat resistance and light resistance of the dye. In order to increase the heat resistance and light resistance of the dye, it is useful to strengthen the bonds between the dye molecules and stabilize the entire crystal. However, if the bond between the dye molecules is strengthened, the solvent molecules are prevented from entering between the dye molecules, and the solubility of the dye is significantly reduced. For this reason, conventionally, in order to increase the solubility of the dye, a solvent having a high dissolving power but difficult to handle from the viewpoint of the environment and safety has been used.

  On the other hand, a water-developable photosensitive coloring composition using water or alcohol as a solvent has been proposed (for example, see Patent Document 2). Such a photosensitive composition mainly uses water as a solvent, is considered to have high environmental characteristics, and has good dye solubility. However, since such a photosensitive composition uses water-soluble components, there has been a problem that these components are less soluble in water due to the influence of dyes and developability is lowered.

  On the other hand, a color filter forming material in which the colorant is a pigment and water is used in an amount of 5 to 100 parts by weight with respect to 100 parts by weight of an organic solvent has been proposed (see, for example, Patent Document 3). However, such a color filter-forming material is intended to improve the dispersibility and storage stability of the pigment, and is not intended to prevent dye precipitation.

  Further, a phthalocyanine-based anionic green dye aqueous solution (an ink composition for a color filter) containing an amide solvent, and a red ink composition for a color filter in which a dye is dissolved in an amide organic solvent aqueous solution (for example, (See Patent Documents 4 and 5.) Although these ink compositions are said to be excellent in dyeability and stability, they were not able to sufficiently suppress dye precipitation. In addition, these methods still have problems in the light resistance and heat resistance of the dye.

  Moreover, the coloring composition which has water or alcohol as a main component as a solvent with water-soluble resin is proposed (for example, refer patent document 6). However, such a composition is an aqueous composition, and similarly, the precipitation of the dye could not be sufficiently suppressed.

As described above, when a photocurable composition is prepared using a dye (particularly a dye having high heat resistance or light resistance), a photocurable composition that can sufficiently suppress the precipitation of the dye has not yet been provided. is the current situation.
JP-A-6-75375 JP 2000-258908 A Japanese Patent Laid-Open No. 9-178923 JP-A-9-291240 JP-A-9-291241 JP 2000-112127 A

A main object of the present invention is to provide a photocurable composition that can be suitably used for a color filter that requires fine pattern formation, such as a color filter for an image sensor, and that is excellent in storage stability.
Another object of the present invention is to provide a high-density and high-resolution color filter using a dye and a method for producing a color filter capable of obtaining the color filter.

  In order to achieve the object of the present invention, as a result of extensive studies by the present inventors, it has been found that a photocurable composition having the following constitution is excellent in storage stability, and has led to the present invention.

  <1> A photocurable composition containing at least an alkali-soluble resin, a dye, a polymerizable monomer, a photopolymerization initiator, and a solvent, wherein at least one of an amide organic solvent and water is used. It is a photocurable composition characterized by containing 3-30 mass% with respect to the total mass of a structural component.

  <2> A photocurable composition containing at least an alkali-soluble resin, a dye, a polymerizable monomer, a photopolymerization initiator, and a solvent, wherein the water content is 3 with respect to the total mass of the constituent components. It is -30 mass%, It is a photocurable composition characterized by the above-mentioned.

  <3> The photocurable composition according to <1> or <2>, wherein the dye is an acid dye.

  <4> The photocurable composition according to any one of <1> to <3>, wherein the dye contains a divalent or higher-valent metal salt.

  <5> The photocurable composition according to <4>, wherein the divalent or higher-valent metal salt includes an azo-based compound or a phthalocyanine-based compound.

  <6> The photocurable composition according to <4> or <5>, wherein the divalent or higher-valent metal salt contains at least one of a γ-acid-azo compound and a pyrazolone azo compound. is there.

〔式中、Ｒ¹は、水素原子、炭素数１〜２１のアルキル基、炭素数１〜２１のアルコキシ基、又は電子吸引性の置換基を表す。Ｒ²は、２価以上の金属原子のカチオンの１価分のカチオンを表す。ｎは０〜５の整数を表す。〕 <7> The photocurable composition according to the above <4> to <6>, wherein the divalent or higher metal salt includes a compound represented by the following general formula (I).

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkoxy group having 1 to 21 carbon atoms, or an electron-withdrawing substituent. R ² represents a monovalent cation of divalent or higher metal atom cations. n represents an integer of 0 to 5. ]

  <8> The photocurable composition according to any one of <1> to <7>, wherein the solvent contains an organic solvent having a boiling point of 80 ° C. to 250 ° C. other than the amide organic solvent. .

  <9> A color filter comprising the photocurable composition according to the above <1> to <8>.

  <10> A method for producing a color filter, wherein the photocurable composition according to the above <1> to <8> is applied onto a substrate, and a pixel is formed on the substrate by a photolithography method.

  ADVANTAGE OF THE INVENTION According to this invention, the photocurable composition which can be used suitably for the color filter which requires fine pattern formation, such as a color filter for image sensors, and was excellent in storage stability can be provided. Furthermore, according to the present invention, it is possible to provide a high-density and high-resolution color filter using a dye, and a color filter manufacturing method capable of obtaining the color filter.

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

<< Photocurable composition >>
The photocurable composition of the present invention is a photocurable composition containing an alkali-soluble resin, a dye, a polymerizable monomer, a photopolymerization initiator, and a solvent, and includes at least an amide organic solvent and water. One (preferably water) is contained in an amount of 3 to 30% by mass with respect to the total mass of the constituent components. That is, the photocurable composition of the present invention contains a specific amount of either an amide-based organic solvent or water, thereby suppressing the precipitation of the dye and improving the storage stability of the composition. In addition, the photocurable composition of the present invention sufficiently prevents the precipitation of the dye even when a dye having high heat resistance and light resistance such as the compound represented by the general formula (1) is used. be able to. For this reason, it can use suitably for preparation of the color filter excellent in heat resistance and light resistance.

Here, “3 to 30% by mass relative to the total mass of the constituent components” means 3 to 30% by mass with respect to the total mass of the photocurable composition of the present invention, that is, the light of the present invention. It is the meaning of 3-30 mass% with respect to the total mass of all the structural components which comprise a curable composition.
In addition, “containing at least one of the amide organic solvent and water in an amount of 3 to 30% by mass with respect to the total mass of the constituent components” means that the total amount of the amide organic solvent and water is the composition of the photocurable composition. It means 3 to 30% by mass relative to the total mass of the components. That is, when either amide organic solvent or water is used alone, it means the total amount of amide organic solvent or water used, and when amide organic solvent and water are used in combination, they are used together. It means the total amount of amide organic solvent and water.

(Amide-based organic solvent / water)
As above-mentioned, the photocurable composition of this invention contains 3-30 mass% with respect to the gross mass of the structural component of a photocurable composition at least any one of an amide type organic solvent and water. When the content of either the amide organic solvent or water, or when these are used in combination, the total content is less than 3% by mass with respect to the total mass of the components of the photocurable composition. When the photocurable composition is prepared, the dye precipitates and a uniform coating film cannot be formed. On the other hand, if the content exceeds 30% by mass, compatibility with other components in the composition becomes difficult, so that coating unevenness occurs during the formation of the coating film, and a uniform coating film cannot be formed in the same manner.

  Examples of the amide organic solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, N, N-diethylformamide, N, N-dimethylpropionamide, N-methyl-ε-. A compound having no active hydrogen such as caprolactam, 1,3-dimethyl-2-imidazolidinone, N, N, N ′, N′-tetramethylurea is preferable from the viewpoint of sufficiently exerting the effect of the present invention. , N-dimethylacetamide and N, N-dimethylformamide are preferred.

  Examples of the water include ion exchange water, distilled water, and ultrafiltration water, and ion exchange water is preferable.

  As at least one of the amide organic solvent and water, water is preferably used alone. When the amide organic solvent and water are used in combination, the ratio (amide organic solvent / water) is preferably 40/60 to 10/90, more preferably 50/50 to 20/80.

(Alkali-soluble resin)
The alkali-soluble resin will be described. The alkali-soluble resin 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. , Maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful. In addition to this, an acid anhydride added to a polymer having a hydroxyl group, polyhydroxystyrene resin, polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol , Etc. are also useful.

The alkali-soluble resin may be copolymerized with a hydrophilic monomer, for example, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary and tertiary. Alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear Propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.
Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid, phosphate ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salts, and monomers containing morpholinoethyl group. is there.

The polymer having a double bond in the molecule can be used as long as it is alkali-soluble and has a double bond such as an ethylenically unsaturated bond. And the like.
The content of the polymer having a double bond in the alkali-soluble resin is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. If the content is less than 10% by mass, the pixel pattern profile may deviate from the rectangle. The content of the double bond in the alkali-soluble resin in the present invention is 1 to 5 mmol / g, preferably 1 to 4.5 mmol / g, more preferably 1.5 to 1 in terms of millimole amount in 1 gram of the resin. 4.0 mmol / g.

Although the example of the polymer containing the said ethylenically unsaturated group is shown below, if a carbon carbon unsaturated bond is contained, it will not be limited to the following.
Examples of the polymer containing an ethylenically unsaturated group include monomers such as 2-hydroxyethyl acrylate having an OH group, methacrylic acid containing a COOH group, and an acrylic or vinyl compound copolymerizable therewith. A compound obtained by reacting an OH group-reactive epoxy ring and a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, in addition to the epoxy ring, a compound having an acid anhydride, an isocyanate group, and an acryloyl group can also be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring disclosed in JP-A-6-102669 and JP-A-6-1938 can be used as a saturated or unsaturated polybasic acid anhydride. A reaction product obtained by reacting a product can also be used. As a compound having both an alkali solubilizing group such as a COOH group and a carbon-carbon unsaturated group, for example, NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co. Ltd.,). ), Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (Daicel UCB Co., Ltd.) ))). Among these, a polymer having at least one selected from a crotonyl group, an acryl group, a methacryl group, an allyl group, a propyl ester group, a vinyl ester group, and an allyloxyalkyl group in a side chain is useful. A polymer having at least one selected from an acryl group, a methacryl group, and an allyl group in the side chain is useful.

  The weight average molecular weight of the alkali-soluble resin in the present invention is preferably 3,000 to 300,000, more preferably 5,000 to 100,000, and particularly preferably 10,000 to 80,000.

  Moreover, 0.5-15 mass% is preferable and, as for content of alkali-soluble resin in the photocurable composition of this invention, 1.0-12 mass% is more preferable. If the content of the alkali-soluble resin is less than 0.5% by mass, the progress of development may be slow, which may increase the production cost. On the other hand, if it exceeds 15% by mass, a good pattern profile may not be obtained.

(dye)
The dye that can be used in the present invention is not particularly limited, and conventionally known dyes for color filters can be used. 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-94821, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215. JP-A-11-343437, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, The dyes disclosed in JP-A-8-302224, JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used. The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.
In the case of a resist system that performs water or alkali development, acidic dyes and / or derivatives thereof may be suitably used 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 can also be used effectively.

  The dye is preferably an acid dye, and is preferably a divalent or higher metal salt. In particular, the divalent or higher metal salt is preferably a divalent or higher metal salt of an acid dye. When the above divalent or higher metal salt is used, high light resistance and high heat resistance, both of which have not been conventionally achieved, can be satisfied at the same time, and performance excellent in pattern formability (developability) and liquid storage stability can be exhibited. The dye in the present invention is preferably an organic solvent-soluble dye that is soluble in an organic solvent.

  The divalent or higher metal salt is a divalent or higher metal salt such as magnesium, calcium, strontium, barium, zinc, aluminum, copper, or iron. Further, the divalent or higher valent metal salt of the acid dye preferably contains at least one of an azo-based compound and a phthalocyanine-based compound, and includes any one of a γ acid-azo compound and a pyrazolone azo compound. Further preferred. Examples of the azo or phthalocyanine compounds include aromatic azo compounds, heteroaromatic azo compounds, metal-phthalocyanine compounds, and the like.

  The divalent or higher metal salt preferably contains a compound represented by the following general formula (I).

In the general formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkoxy group having 1 to 21 carbon atoms, or an electron-withdrawing substituent. R ² represents a monovalent cation of a divalent or higher valent metal atom. n represents an integer of 0 to 5.

The alkyl group having ¹ to 21 carbon atoms represented by R ¹ may have a substituent, and an alkyl group having 1 to 15 carbon atoms is more preferable. The alkyl group having ¹ to 21 carbon atoms represented by R ¹ may be a linear, branched, or cyclic alkyl group. For example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n- Amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n- Pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1- Methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3- Methylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethyl Hexyl group, t-octyl group, branched nonyl group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, branched pentadecyl group, branched hexadecyl group, branched Heptadecyl group, branched octadecyl group, linear or branched nonadecyl group, linear or branched eicosanyl group,

Cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, cis -Miltanyl group, isopinocamphenyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentylethyl group, bicyclooctyl group preferable.

Among these, as a C1-C21 alkyl group represented by said R < ¹ >, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl Group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, i-propyl group, sec-butyl group, i-butyl Group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl Group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethyl Hexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, cyclopropyl group, Cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, cis-miltanyl group, More preferred are isopinocanphenyl, noradamantyl, adamantyl, adamantylmethyl, 1- (1-adamantyl) ethyl, 3,5-dimethyladamantyl, quinuclidinyl, cyclopentylethyl, and bicyclooctyl. Among these, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n- Decyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2 -Dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, straight Chain or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, cyclopropyl group, Ropropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, noradamantyl group, adamantyl Group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, cyclopentylethyl group and bicyclooctyl group are particularly preferred.

  Further, among the above groups, in order to improve heat resistance, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl group, n-decyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl Group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2- Methylpropyl, branched heptyl, 1-methylheptyl, 1,5-dimethylhexyl, t-octyl, branched nonyl, branched decyl, cyclopropyl, cyclopropylmethyl, cycl Butyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, noradamantyl group, adamantyl group, adamantylmethyl group Particularly preferred are branched alkyl groups and cyclic alkyl groups such as 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, cyclopentylethyl group, and bicyclooctyl group.

The alkyl group represented by R ¹ may contain an ether group, such as a tetrahydrofurfuryl group, a tetrahydropyranylmethyl group, a 2,5-dihydro-2,5-dimethoxyfurfuryl group, and the like. preferable.

The alkyl group represented by R ¹ may be an alkyl group substituted with fluorine. Examples of the alkyl group substituted with fluorine include trifluoromethyl group, trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadeca group. A fluorooctyl group, a tridecafluorooctyl group, a nonadecafluorononyl group, a heptadecafluorodecyl group, and a perfluorodecyl group are preferable, and among them, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group Group, tridecafluorohexyl group and pentadecafluoroheptyl group are more preferable, and trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group and tridecafluorohexyl group are particularly preferable. There.

In said general formula (I), the C1-C21 alkoxy group represented by R < ¹ > may have a substituent, and a C1-C15 alkoxy group is still more preferable.
The alkoxy group of 1 to 21 carbon atoms represented by R ^1, group linked to an alkyl group represented by R ¹ described above with an oxygen atom (alkyl group) is preferable. The preferable range in this is the same as the preferable example of the above-mentioned alkyl group.

In the general formula (I), the electron-withdrawing substituent represented by R ¹ is not particularly limited as long as it is electron-withdrawing.
As the electron-withdrawing group represented by R ¹ , the Hammett's σ value described in “Hammett's rule-structure and reactivity-” written by Naoki Inamoto and Maruzen Co., Ltd. has a positive value. There is no limitation. Examples of the electron withdrawing group include ethynyl group, trifluoromethyl group, cyano group, formyl group, acyl group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, nitro group, acetoxy group, mercapto group, alkylthio group. Group, alkylsulfinyl group, substituted sulfonyl group (alkylsulfonyl group, arylsulfonyl group, etc.), sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acylthio group, fluoro group, chloro group, bromo group, iodo group Among these, ethynyl, trifluoromethyl, cyano, acyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, nitro, acetoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, More preferred are sulfonylsulfonyl groups, sulfamoyl groups, substituted sulfamoyl groups (alkylsulfamoyl groups, arylsulfamoyl groups, etc.), fluoro groups, chloro groups, bromo groups, iodo groups, trifluoromethyl groups, cyano groups, acyl groups. Carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, nitro group, acetoxy group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, etc., sulfamoyl group, substituted sulfamoyl group (alkylsulfamoyl group, arylsulfuryl group) Famoyl group etc.), fluoro group, chloro group, bromo group are particularly preferred.

  These electron-withdrawing groups are further similar substituents, as well as acyl groups, acylamino groups, acylaminocarbonylamino groups, aralkylaminocarbonylamino groups, arylaminocarbonylamino groups, methacryloylaminocarbonylamino groups, trifluoromethyl groups, Fluoro group, chloro group, bromo group, iodo group, hydroxy group, nitro group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, vinyl group, methoxy group, ethoxy group, butoxy group, isopropoxy group, t-butoxy group, cyclohexyloxy group, vinyloxy group, phenyloxy group, methylthio group , Ethylthio group, pyrrolidinyl group, piperidinyl group, amino Group, dimethylamino group, diethylamino group, may be substituted with a phenyl group.

The (substituted) sulfamoyl group mentioned as a preferred example of the electron-withdrawing substituent represented by R ¹ is preferably a (substituted) sulfamoyl group represented by the following general formula (II).

〔式中、Ｒ³及びＲ⁴は、それぞれ独立して、水素原子、炭素数１〜２１のアルキル基、炭素数２〜２１のアルケニル基、炭素数６〜２１のアリール基、又は炭素数７〜２１のアラルキル基を表す。Ｒ³及びＲ⁴は置換基を有していてもよい。また、Ｒ³，Ｒ⁴が置換している窒素原子と一緒になって、ヘテロ環を形成してもよい。〕

[Wherein, R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, an aryl group having 6 to 21 carbon atoms, or 7 carbon atoms. Represents an aralkyl group of ˜21. R ³ and R ⁴ may have a substituent. Further, R ³ and R ⁴ may be combined with the substituted nitrogen atom to form a heterocycle. ]

In general formula (II), the C1-C21 alkyl group represented by R < ³ > and R < ⁴ > may have a substituent and is preferably a C1-C15 alkyl group.
The alkyl group having 1 to 21 carbon atoms represented by R ³ and R ⁴ may be a linear, branched or cyclic alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3- Dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5- Dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, branched pentadecyl group, branched hexadecyl group, branched Heptadecyl group, branched octadecyl group, linear or branched nonadecyl group, linear or branched eicosanyl group,

Cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, cis -Miltanyl group, isopinocamphenyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentylethyl group, bicyclooctyl group preferable.

Among these, as a C1-C21 alkyl group represented by said R < ³ > and R < ⁴ >, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-amyl group, n-, for example Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, i-propyl, sec- Butyl, i-butyl, t-butyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, i-amyl, neopentyl, 1,2-dimethylpropyl, 1,1-dimethyl Propyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylhept Tyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group , Cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, Cis-miltanyl group, isopinocanphenyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentylethyl group, bicyclothio A til group is more preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, n -Decyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1, 2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, Linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, cyclopropyl group Cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, noradamantyl group, adamantyl group Group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, cyclopentylethyl group and bicyclooctyl group are particularly preferred.

  Furthermore, among the above groups, in order to improve heat resistance, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n -Nonyl group, n-decyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, Neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2 -Methylpropyl group, branched heptyl group, 1-methylheptyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, cyclopropyl group, cyclopropylmethyl group, Robutyl, cyclobutylmethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cycloheptyl, cyclooctyl, cyclohexylpropyl, cyclododecyl, norbornyl, bornyl, noradamantyl, adamantyl, adamantylmethyl Particularly preferred are branched alkyl groups and cyclic alkyl groups such as 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, cyclopentylethyl group, and bicyclooctyl group.

In the general formula (II), the alkyl group represented by R ³ and R ⁴ may be an alkyl group substituted with fluorine. Examples of the alkyl group substituted with fluorine include trifluoromethyl group, trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadeca group. A fluorooctyl group, a tridecafluorooctyl group, a nonadecafluorononyl group, a heptadecafluorodecyl group, and a perfluorodecyl group are preferable, and among them, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group Group, tridecafluorohexyl group, and pentadecafluoroheptyl group are more preferable, and further, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, and tridecafluorohexyl group are preferable. Preferred.

In the general formula (II), the alkenyl group having 2 to 21 carbon atoms represented by R ³ and R ⁴ may have a substituent, and an alkenyl group having 2 to 15 carbon atoms is more preferable.
Examples of the alkenyl group having 2 to 21 carbon atoms represented by R ³ and R ⁴ include a vinyl group, an isopropenyl group, a 2-propenyl group, a 2-methyl-propenyl group, and a 1-methyl-1-propenyl group. 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 2,6-dimethyl-5-heptenyl group, 9-decenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl-2-cyclo A hexenyl group, an octenyl group, a citronellyl group, an oleyl group, a geranyl group, a farnesyl group, and a 2- (1-cyclohexenyl) ethyl group are preferable, and among these, vinyl Group, isopropenyl group, 2-propenyl group, 2-methyl-propenyl group, 1-methyl-1-propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1,1- Dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclo More preferred are a hexenyl group and a 1-methyl-2-cyclohexenyl group, and further a vinyl group, an isopropenyl group, a 2-propenyl group, a 2-methyl-propenyl group, a 1-methyl-1-propenyl group, and a 1-butenyl. Group, 3-butenyl group, 1-methyl-1-butenyl group, 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl 1-pentenyl group, 1-hexenyl group, 1-cyclopentenyl group, 2-cyclopentenyl methyl, cyclohexenyl group, 1-methyl-2-cyclohexenyl group particularly preferred.

The aryl group having 6 to 21 carbon atoms represented by R ³ and R ⁴ may have a substituent, and is preferably an aryl group having 6 to 15 carbon atoms.
Examples of the aryl group having 6 to 21 carbon atoms which may have a substituent represented by R ³ and R ⁴ include phenyl group, naphthyl group, biphenylenyl group, acenaphthenyl group, fluorenyl group, anthracenyl group, anthraquinonyl Group, pyrenyl group and the like are preferable, and among them, phenyl group, naphthyl group, biphenylenyl group, acenaphthenyl group, fluorenyl group, anthracenyl group and the like are more preferable, and further, phenyl group, naphthyl group, biphenylenyl group, fluorenyl group and the like are particularly preferable. preferable.

The aralkyl group having 7 to 21 carbon atoms represented by R ³ and R ⁴ may have a substituent, and an aralkyl group having 7 to 15 carbon atoms is more preferable.
Examples of the aralkyl group having 7 to 21 carbon atoms which may have a substituent represented by R ³ and R ⁴ include benzyl group, diphenylmethyl group, 1,2-diphenylethyl group, phenyl-cyclopentylmethyl. Group, α-methylbenzyl group, phenylethyl group, α-methyl-phenylethyl group, β-methyl-phenylethyl group, 3-phenylpropyl group, 3,3-diphenylpropyl group, 4-phenylbutyl group, naphthylmethyl Group, styryl group, cinnamyl group, fluorenyl group, 1-benzocyclobutenyl group, 1,2,3,4-tetrahydronaphthyl group, indanyl group, piperonyl group and pyrenemethyl group are preferable, among which benzyl group, phenyl- Cyclopentylmethyl group, α-methylbenzyl group, phenylethyl group, α-methyl-phenylethyl group β-methyl-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group, styryl group, cinnamyl group, fluorenyl group, 1-benzocyclobutenyl group, 1,2,3,4-tetrahydronaphthyl group More preferably, benzyl group, α-methylbenzyl group, phenylethyl group, α-methyl-phenylethyl group, β-methyl-phenylethyl group, 3-phenylpropyl group, styryl group, cinnamyl group, fluorenyl group, 1 -A benzocyclobutenyl group and a 1,2,3,4-tetrahydronaphthyl group are particularly preferred.

The alkyl group, alkenyl group, aryl group and aralkyl group represented by R ³ and R ⁴ may contain an ether group, for example, tetrahydrofurfuryl group, tetrahydropyranylmethyl group, 2,5-dihydro group. A -2,5-dimethoxyfurfuryl group and the like are also preferable.

Examples of forming a heterocycle together with the nitrogen atom substituted by R ³ and R ⁴ are 2-methylaziridine ring, azetidine ring, pyrrolidine ring, 3-pyrroline ring, piperidine ring, 2,3,6-tetrahydropyridine ring, hexamethyleneimine ring, piperazine ring, 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane ring, decahydroquinoline ring, oxazolidine ring, morpholine ring, Thiazolidine ring, thiomorpholine ring, indoline ring, isoindoline ring, 1,2,3,4-tetrahydrocarbazole ring, 1,2,3,4-tetrahydroquinoline ring, 1,2,3,4-tetrahydroisoquinoline ring, An iminodibenzyl ring, a phenoxazine ring, a phenothiazine ring, a phenazine ring and the like are preferable. Among them, a pyrrolidine ring, 3 -Pyrroline ring, piperidine ring, 1,2,3,6-tetrahydropyridine ring, hexamethyleneimine ring, piperazine ring, decahydroquinoline ring, oxazolidine ring, morpholine ring, thiazolidine ring, thiomorpholine ring, etc. are more preferable. Particularly preferred are pyrrolidine ring, 3-pyrroline ring, piperidine ring, 1,2,3,6-tetrahydropyridine ring, piperazine ring, decahydroquinoline ring, oxazolidine ring, morpholine ring, thiazolidine ring, thiomorpholine ring and the like.

In the general formula (II), an alkyl group, an alkenyl group, an aryl group, an aralkyl group represented by R ³ and R ⁴ , or R ³ and R ⁴ are formed together with a substituted nitrogen atom. Heterocyclic substituents include acyl, acylamino, acylaminocarbonylamino, aralkylaminocarbonylamino, arylaminocarbonylamino, methacryloylaminocarbonylamino, trifluoromethyl, fluoro, chloro, bromo Group, iodo group, hydroxy group, nitro group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, Hexyl, heptyl, octyl, vinyl, methoxy, ethoxy, butoxy, isopropoxy, t-butyl Xyl group, cyclohexyloxy group, vinyloxy group, methylthio group, ethylthio group, pyrrolidinyl group, piperidinyl group, amino group, dimethylamino group, diethylamino group, phenyl group and the like are preferable. Among them, acyl group (especially acetyl group), acylamino group are preferable. Group, trifluoromethyl group, fluoro group, chloro group, bromo group, hydroxy group, nitro group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec- Butyl, t-butyl, pentyl, hexyl, vinyl, methoxy, ethoxy, butoxy, isopropoxy, t-butoxy, cyclohexyloxy, vinyloxy, methylthio, ethylthio, pyrrolidinyl Piperidinyl group, amino group, dimethylamino group, diethyla Mino group, phenyl group and the like are more preferable, and further, acyl group (particularly acetyl group), acylamino group, trifluoromethyl group, fluoro group, chloro group, bromo group, hydroxy group, nitro group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, vinyl group, methoxy group, ethoxy group, isopropoxy group, cyclohexyloxy group, vinyloxy group, methylthio group , Ethylthio group, pyrrolidinyl group, piperidinyl group, amino group, dimethylamino group, diethylamino group, phenyl group and the like are particularly preferable.
Moreover, these substituents may be further substituted with the same substituent.

  In particular, when the substituent is a group having an active hydrogen such as a hydroxy group or an amino group, it is reacted with various acid chlorides, acid anhydrides, halides or various isocyanates to give an acetyl group, an acyl group, (meth) It may be substituted with a group such as acryloyl group, alkylaminocarbonyl group, arylaminocarbonyl group (for example, butylaminocarbonyl group, phenylaminocarbonyl group, etc.), alkyl group, aralkyl group and the like.

Further, the alkyl group, alkenyl group, aryl group, aralkyl group represented by R ³ and R ⁴ , or the heterocyclic ring formed together with the nitrogen atom substituted by R ³ and R ⁴ is further described above. And may be substituted with a group represented by R ^{3 or} R ⁴ .

In terms of color values, the molecular weight of the group represented by R ³ and R ⁴ is preferably 500 or less together R ³ and R ^4, and more preferably 400 or less, particularly preferably 300 or less.
The number of substituents R ³ and R ⁴ is preferably 0-4, more preferably 0-3, particularly preferably 0-2.

In the general formula (I), examples of the substituent for the group represented by R ¹ include an acyl group, an acylamino group, an acylaminocarbonylamino group, an aralkylaminocarbonylamino group, an arylaminocarbonylamino group, and a methacryloylaminocarbonylamino group. Group, trifluoromethyl group, fluoro group, chloro group, bromo group, iodo group, hydroxy group, nitro group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group , Sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, vinyl group, methoxy group, ethoxy group, butoxy group, isopropoxy group, t-butoxy group, cyclohexyloxy group, vinyloxy group , Methylthio group, ethylthio group, pyrrolidinyl group, piperidinyl group, amino group, di Preferred are a tilamino group, a diethylamino group, a phenyl group, etc. Among them, an acyl group (particularly an acetyl group), an acylamino group, a trifluoromethyl group, a fluoro group, a chloro group, a bromo group, a hydroxy group, a nitro group, a methyl group, and an ethyl group Group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, vinyl group, methoxy group, ethoxy group, butoxy group, An isopropoxy group, t-butoxy group, cyclohexyloxy group, vinyloxy group, methylthio group, ethylthio group, pyrrolidinyl group, piperidinyl group, amino group, dimethylamino group, diethylamino group, phenyl group and the like are more preferable, and an acyl group (Especially acetyl group), acylamino group, trifluoromethyl group, fluoro group, Chloro group, bromo group, hydroxy group, nitro group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, vinyl group, methoxy Particularly preferred are a group, an ethoxy group, an isopropoxy group, a cyclohexyloxy group, a vinyloxy group, a methylthio group, an ethylthio group, a pyrrolidinyl group, a piperidinyl group, an amino group, a dimethylamino group, a diethylamino group, and a phenyl group.
Moreover, these substituents may be further substituted with the same substituent.

In particular, in the above general formula (I), when the substituent of the group represented by R ¹ is a group having active hydrogen such as a hydroxy group or an amino group, various acid chlorides, acid anhydrides, halides or various isocyanates With acetyl group, acyl group, (meth) acryloyl group, alkylaminocarbonyl group, arylaminocarbonyl group (eg, butylaminocarbonyl group, phenylaminocarbonyl group, etc.), alkyl group, aralkyl group, etc. May be substituted.

Further, from the viewpoint of color value, the molecular weight of the group represented by R ¹ in the general formula (I) is preferably 700 or less, more preferably 600 or less, and particularly preferably 500 or less.

R ² in the general formula (1) represents a monovalent cation of a divalent or higher valent metal atom. As the ^{R 2, 1 / 2Mg +,} 1 / 2Ca +, 1 / 2Sr +, 1 / 2Ba +, 1 / 2Zn +, 1 / 3Al +, 1 / 2Cu +, preferably 1 / 2Fe ^+, etc., this Among these, 1 / 2Mg ⁺ , 1 / 2Ca ⁺ , 1 / 2Ba ⁺ , 1 / 2Zn ⁺ , 1 / 3Al ⁺ , 1 / 2Cu ⁺ , 1 / 2Fe ^+, etc. are more preferable, and 1 / 2Mg ⁺ , 1 / 2Ca ⁺ , 1 / 2Ba ⁺ , 1 / 2Zn ⁺ , 1 / 3Al ⁺ , 1 / 2Cu ⁺ , and the like are particularly preferable.

In the general formula (I), n represents the number of substituents represented by R ¹ . In general formula (I), n is 0-5, 0-4 are preferable, 0-3 are more preferable, and 0-2 are especially preferable.

The compound represented by the general formula (I) may be used in combination with a compound in which the portion corresponding to R ² is a monovalent metal cation or a cation composed of a nitrogen-containing compound.
In that case, the portion corresponding to R ² in the general formula (I) of the compound is preferably a hydrogen atom, Na, K, Rb, Cs, Ag, or a cation composed of a nitrogen-containing compound, and among these, a hydrogen atom, Na , K, Rb, Ag, or a cation comprising a nitrogen-containing compound is more preferred, and a cation comprising a hydrogen atom, Na, Ag, or a nitrogen-containing compound is particularly preferred.

The nitrogen-containing compound is selected in consideration of all of the solubility in organic solvents and water, salt-forming properties, dye absorbance and color value, heat resistance and light resistance. When selected only from the viewpoint of absorbance and color value, the nitrogen-containing compound preferably has a molecular weight as low as possible. Among them, the molecular weight is preferably 300 or less, more preferably 280 or less, and molecular weight 250 or less. It is particularly preferred that
Specific examples of the nitrogen-containing compound described above are listed below, but the present invention is not limited thereto.

  Although the specific example (exemplary compound (1)-(8)) of a compound represented by the said general formula (I) below is given, this invention is not limited to this.

  The dye represented by the general formula (1) can be synthesized by a known general method. Hereinafter, a general synthesis method of the dye represented by the general formula (1) will be described by taking the exemplified compound (1) as an example. However, the present invention is not limited to this.

  The exemplary compound (1) can be produced according to the following scheme 1.

  First, the compound (A), cyclohexylmethyl bromide, dimethylformamide (DMF), and triethylamine are mixed and stirred at about 50 ° C. for several hours. The reaction mixture is then poured into water and extracted with ethyl acetate, and the ethyl acetate phase is washed several times with water. Thereafter, magnesium sulfate and activated carbon are added to the ethyl acetate phase, dried, decolorized, filtered, the ethyl acetate phase is concentrated, and the above compound (B) can be obtained by recrystallization from hexane / ethyl acetate.

  Next, o-nitrobenzenesulfonyl chloride and acetone are mixed and dissolved, and the compound (B) is gradually added. Thereafter, the mixture is heated and a 20% aqueous sodium carbonate solution is added dropwise, followed by stirring for about 1 hour, heating, and further stirring for about 1 hour. After stirring, the reaction mixture is poured into water and extracted with ethyl acetate, and the ethyl acetate phase is washed with 4% aqueous sulfuric acid. Further, magnesium sulfate and activated carbon are added to the ethyl acetate phase, dried, decolorized, filtered, and the ethyl acetate phase is concentrated to obtain the compound (C).

  Next, reduced iron, acetic acid and water are mixed and stirred while heating, and then a dichlorobenzene solution of the obtained compound (C) is added dropwise and stirred for several hours while heating. After stirring, sodium carbonate is further added and stirred for about 30 minutes while heating. Celite and activated carbon are added and filtered, and then the organic layer is subjected to steam distillation to obtain the compound (D).

Next, the obtained compound (D), tetraethylammonium chloride, acetic acid and 36% hydrochloric acid are mixed and cooled to about 0 ° C. After cooling, the sodium nitrite aqueous solution is dropped while maintaining the internal temperature at 5 ° C. or lower, and the mixture is stirred while maintaining the temperature at about 5 to 10 ° C.
Next, the above solution is dropped into a separately prepared alkaline aqueous solution of γ acid, and a 40% aqueous sodium acetate solution is further dropped, followed by stirring at about 0 ° C. for several hours. After stirring, a 10% aqueous sodium carbonate solution is added dropwise and stirred overnight, then a 50% aqueous NaOH solution is added dropwise, followed by stirring for about one hour while warming, and then cooling to room temperature. The compound (E) can be obtained by filtering the mixture and washing with an alkaline saline solution.

Next, the obtained compound (E) is dissolved in MeOH, and water is added to this solution and stirred. After stirring, add MgSO ₄ and further stir, let stand overnight, then add ethyl acetate. After the addition of ethyl acetate, the above exemplified compound (1) can be obtained by filtering to remove MgSO ₄ and concentrating the MeOH solution.
Other exemplified compounds can also be synthesized by the above-described method by appropriately selecting materials and the like.

  The above divalent or higher metal salt is a salt of another acid dye, another acid dye and a metal or a nitrogen-containing compound (these may be simply referred to as “atomic groups forming a salt with the acid dye”), Or you may use simultaneously with the derivative | guide_body of other acidic dyes, etc.

~ Acid dye ~
The acid dye will be described. The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in organic solvents and developers, salt-forming properties, absorbance, and other components in the curable composition. Are selected in consideration of all the required performances such as the interaction, light resistance, heat resistance and the like.
Although the specific example of the said acidic dye is given to the following, it is not limited to these. For example, acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,45,62,70,74,80,83,86,87,90,92,103,112,113,120, 129, 138, 147, 158, 171, 182, 192;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50;
acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95;
acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252 257, 260, 266, 274;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,134, 172, 228, 38, 65, 220, 169, 243;
Food Yellow 3;
And derivatives of these dyes.

Among these, as the acid dye,
acid black 24;
acid blue 23, 25, 29, 62, 86, 87, 92, 138, 158;
acid orange 8, 51, 56, 74, 63, 74;
acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217;
acid violet 7;
Acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 172, 228, 38, 65, 220, 169, 243 and the like and derivatives of these dyes Is preferred.

In addition, as the acid dye, other than the dyes exemplified above, azo, xanthene, and phthalocyanine acid dyes are also preferable.
C. I. Solvent Blue 44, 38, C.I. I. Solvent Orange 45, Rhodamine B, Rhodamine 110, 2,7-Naphthalenedisulfonic acid, 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5- [minyl] ulyl , Etc. and derivatives of these dyes are also preferably used.
As the derivative of the acid dye, a compound obtained by converting the sulfonic acid of the acid dye into a sulfonic acid amide or a sulfonic acid ester can be suitably used.

~ About atomic groups that form salts with acid dyes ~
The atomic group that forms a salt with the acidic dye is not particularly limited as long as it is a cationic group that forms a salt with the anion of the acidic dye. Examples of the atomic group include a hydrogen atom, Na, K, Rb, Cs, and a cation composed of a nitrogen-containing compound.
The nitrogen-containing compound that forms a counter salt with the acid dye will be described. In the present invention, the nitrogen-containing compound that forms a salt with the acidic dye has all of the solubility in organic solvents and developer, the salt-forming property, the absorbance of the dye, the interaction with other components in the curable composition, etc. Selected in consideration. When selected only from the viewpoint of absorbance, those having a molecular weight as low as possible are preferred. Among them, the molecular weight is preferably 245 or less, more preferably 240 or less, and particularly preferably 230 or less.

Further, in order to prevent light fading and improve heat resistance of the dye, a nitrogen-containing compound generally known as an anti-fading agent may be used. In this respect, the acid value potential is lower (the ionization potential is smaller). Compounds, tertiary amine compounds, aliphatic cyclic amine compounds, aniline compounds, hydrazine compounds, and the like are preferable.
Preferred specific examples of these nitrogen-containing compounds are the same as those mentioned above.

-About the ratio (m) of the acid dye and the salt forming atomic group to the acid dye-
The ratio of the atomic group forming the salt with the acid dye / acid dye (hereinafter referred to as “m”) will be described. The m is a value that determines the molar ratio between the acid dye molecule and the atomic group that is a counter ion, and can be freely selected according to the salt forming conditions of the acid dye atomic group. Specifically, it is a numerical value between 0 ≦ m ≦ 10 of the number of functional groups of the acid in the acid dye, solubility in organic solvents and developers, salt formation, absorbance, other components in the curable composition It is selected in consideration of all necessary performance priorities such as interaction with light, light resistance, and heat resistance. From the standpoint of absorbance only, m is preferably a value between 0 ≦ m ≦ 7, more preferably a value between 0 ≦ m ≦ 6, and a range between 0 ≦ m ≦ 5. It is particularly preferable to take a numerical value.

~ Use concentration ~
Next, the use concentration of the dye in the present invention will be described. The concentration of the colorant used in the present invention relative to the total solid components of the photocurable composition of the present invention varies depending on the type of dye used and the like, but is preferably 0.5 to 80% by mass, and 0.5 to 60% by mass. More preferably, 0.5-50 mass% is especially preferable. When the use concentration of the colorant is in the range of 0.5 to 80 mass%, the curability and developability of the photocurable composition can be improved.

(Polymerizable monomer)
Next, the polymerizable monomer will be described. As the polymerizable monomer, a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure is preferable. Monofunctional acrylates and methacrylates such as (meth) acrylate, polypropylene glycol mono (meth) acrylate, 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) Ethylene oxide and propylene oxide were added to polyfunctional alcohols such as acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane Later (meth) acrylates, urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183 Polyfunctional acrylates such as polyester acrylates described in JP-B-49-43191 and JP-B-52-30490, epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, Metaac Rate and can be exemplified mixtures thereof. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  The content of the polymerizable monomer in the photocurable composition of the present invention is preferably 0.1 to 90 mass%, more preferably 1.0 to 80 mass%, and 2.0 to 70 mass% with respect to the solid content. % Is particularly preferred.

(Photopolymerization initiator)
Next, the photopolymerization initiator will be described. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable monomer and the alkali-soluble resin, but is a trihalomethyltriazine type in terms of polymerization characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. Including at least one compound selected from the group consisting of a compound, an oxime compound, and an α-aminoketone compound is essential to obtain the effects of the present invention.

  As photopolymerization initiators of halomethyl-s-triazine compounds, vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho-) described in JP-A-53-133428 are disclosed. 1-yl) -4,6-bis-halomethyl-s-triazine compounds and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compounds.

  Other examples include TAZ series, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, and TAZ-104 manufactured by Midori Chemical. .

  Examples of photopolymerization initiators for α-aminoketone compounds include Irgacure series, Irgacure 907, Irgacure 369, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1- manufactured by Ciba Geigy. [4- (Hexyl) phenyl] -2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like.

  Although it does not specifically limit as a photoinitiator of an oxime type compound, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl) -Phenyl) -butane-1,2-butane 2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) ) -Acetic acid ethyl ester-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate, and the like.

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, dibenzalacetone, 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 photopolymerization initiators, 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-aminophenyl ketone combination, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Examples include teal-s-triazine compounds.
Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound, a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, an acetophenone compound, and Examples thereof include cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

Alternatively, active halogen compounds such as halomethyloxadiazole can also be used effectively. Examples thereof include 2-halomethyl-5-vinyl-1,3,4-described in JP-B-57-6096. Oxadiazole compounds, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, And 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole.
Further, as the photopolymerization initiator, T series manufactured by PANCHIM can also be used effectively, and examples thereof include T-OMS, T-BMP, TR, and TB.
Further, as the photopolymerization initiator, Irgacure series manufactured by Ciba Geigy can be used effectively. Examples of these include Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, Darocure series, Darocure 1173, etc. may be mentioned.
Other examples of the photopolymerization initiator include 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- Benzyl-2-dimethylamino-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 usefully used.

  The amount of the photopolymerization initiator used in the photocurable composition of the present invention is preferably 0.01% by mass to 50% by mass and more preferably 1% by mass to 30% by mass with respect to the solid content of the polymerizable monomer. Preferably, 1% by mass to 20% by mass is particularly preferable. When the amount of the photopolymerization initiator used is less than 0.01% by mass, the polymerization is difficult to proceed, and when it exceeds 50% by mass, the polymerization rate increases, but the molecular weight decreases and the film strength may decrease.

  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-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. Useful.

(solvent)
The solvent used in the photocurable composition of the present invention is not particularly limited as long as it satisfies the solubility and coating properties of the photocurable composition of the present invention, but in particular, dyes and binders (alkali-soluble resins). It is preferable to select it in consideration of solubility, applicability, and safety.
Solvents that can be used in preparing the photocurable composition of the present invention include various organic solvents, such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate , Methyl ethoxyacetate, ethyl ethoxyacetate,

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 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, 2-ethoxy-2-methylpropionic acid ethyl,

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 mono Ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,

Propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene, Examples include xylene.

  Of these, the organic solvents include methyl 3-ethoxypropionate, ethyl 3-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, propylene glycol methyl ether acetate and the like are more preferable.

  Especially, as said solvent, what contains the organic solvent with a boiling point of 80 to 250 degreeC as organic solvents other than an amide type organic solvent from a viewpoint of the applicability | paintability of a photocurable composition is preferable. This is because, when an amide organic solvent is used as the organic solvent, when a color filter is produced by a photolithographic method when used alone or mainly, a pixel of another color is formed on the formed pixel. This is because the formed image may be damaged. Moreover, when the boiling point is in the range of 80 ° C. to 250 ° C., the drying property of the coating solution is increased due to the low boiling point of the solvent, and it becomes difficult to form a uniform coating film. By being high, it is possible to prevent the drying property of the coating liquid from being lowered, the drying load being increased, and the process suitability and the manufacturing cost from being increased.

  The boiling point of the organic solvent other than the amide organic solvent is preferably 90 ° C. to 230 ° C., more preferably 100 to 200 ° C. Moreover, as a ratio of 80 to 250 degreeC organic solvents other than the amide type organic solvent in all the solvents, 60 to 96 mass% is preferable, and 65 to 95 mass% is still more preferable.

  Examples of the organic solvent at 80 ° C. to 250 ° C. other than the amide organic solvent include, for example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy Methyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are preferable.

(Other additives)
In the photocurable composition of the present invention, various additives as necessary, for example, fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. Can be blended.

  Specific examples of these 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.

  In the case where the alkali solubility of the non-irradiated part is promoted and the developability of the photocurable composition of the present invention is further improved, the photocurable composition of the present invention is preferably an organic carboxylic acid, preferably Addition of a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less can be performed. Specifically, 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, glutar Aliphatic dicarboxylic acids such as 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 carbaryl 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, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa 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》
The color filter of the present invention is produced using the above-described photocurable composition of the present invention. In the method for producing a color filter of the present invention, the photocurable composition of the present invention is applied on a substrate, and pixels are formed on the substrate by photolithography. Specifically, a coating step of coating the photocurable composition of the present invention directly or via another layer on a substrate, a step of drying to form a coating film (prebaking step), and the coating film Further, a step of exposing a specific pattern (exposure step), a step of developing the exposed coating film with an alkaline developer (developing step), and a step of heating the developed coating film (Post-baking step) is preferably included, and a colored pattern can be formed through these steps. Moreover, the manufacturing method of the color filter of this invention may include the process of hardening the said resist pattern by heating and exposure as needed.

In the coating step, the photocurable composition of the present invention is applied on a substrate by a coating method such as spin coating, casting coating, roll coating, slit coating, and the like to form a coating film on the substrate. The coating film is dried in the prebaking step to form a radiation-sensitive photocurable composition film.
Examples of the substrate include soda glass, Pyrex (R) glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, and photoelectric conversion element substrates used for imaging elements, such as silicon. Examples include a substrate and the like, and a complementary metal oxide semiconductor (CMOS). These substrates may have a black matrix that optically isolates each pixel.
If necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.

  The said exposure process exposes a specific pattern to a photocurable composition film formed on the board | substrate through a mask etc., for example. As radiation used for exposure, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

The development step is a step of developing the exposed coating film with an alkaline developer. Any alkali developer may be used as long as it dissolves the photocurable composition of the present invention and does not dissolve the exposed portion (radiation irradiated portion). Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
As said organic solvent, the above-mentioned 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. And hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, and the like.

The alkaline developer used in the present invention is preferably an alkaline aqueous solution adjusted to have an alkali concentration of preferably pH 11 to 13, more preferably pH 11.5 to 12.5. If the alkali concentration exceeds pH 13, pattern roughness, peeling, and a decrease in the remaining film ratio may occur. If the pH is less than 11, the development speed may be reduced or generation of residues may be observed. .
In the development step, development processing is performed with a developer composed of such an alkaline aqueous solution. Examples of the development method include a dipping method, a spray method, a paddle method, and the like, and the temperature is preferably 15 to 40 ° C. In addition, after development, washing is generally performed with running water.

Furthermore, in the method for producing a color filter of the present invention, heat treatment is performed in a post-baking process in order to sufficiently cure the coated film after development. 100-300 degreeC is preferable and the heating temperature in the said heating process has more preferable 150-250 degreeC. The heating time is preferably about 10 minutes to 1 hour, more preferably about 5 minutes to 30 minutes.
The color filter manufacturing method of the present invention is a post-cure that further accelerates curing of each pixel formed by irradiating the entire surface of the developed color filter pixel pattern with radiation such as ultraviolet rays before the post-baking step. You may give a process. According to the post-cure process, it is possible to prevent the profile of the pixel pattern from being lost in the post-bake process. In particular, when the colorant is a dye as in the present invention, the collapse of the pattern profile in the post-baking process tends to be a problem compared to the case where the colorant is a pigment. Therefore, the post-cure process is an effective process for producing a color filter for an image sensor using a dye as a colorant.

  The color filter of the present invention is used for an image sensor such as a CCD, and is particularly suitable for a high-resolution CCD element or CMOS element exceeding 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 collecting light.

  EXAMPLES 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 of the present invention. Unless otherwise specified, “part” is based on mass.

[Example 1]
1) Preparation of photocurable composition The following composition was mixed and melt | dissolved and the photocurable composition was prepared.
<composition>
Solvent 760 parts Ethyl lactate Alkali-soluble resin 59 parts Benzyl methacrylate / methacrylic acid copolymer (60/40 copolymer ratio, acid value 100 mg KOH / g average molecular weight 30,000)
・ Polymerizable monomer 88 parts Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
Photopolymerization initiator 13 parts Trichlorotriazine compound (TAZ-107: manufactured by Midori Chemical Co., Ltd.)
Dye 40 parts Acid red 57 (Mg salt: the above exemplified compound (1))
・ 40 parts of ion exchange water

2) Production of silicon wafer substrate with undercoat layer Undercoat resin CT2000L (manufactured by FUJIFILM Arch Corporation) was applied on a 10 cm × 10 cm glass plate 1737 (manufactured by Corning) so that the dry film thickness was 2 μm. The glass plate with an undercoat layer was obtained by heating and drying in an oven at 220 ° C. for 1 hour.

3) Exposure / development of photocurable coating film The photocurable composition obtained in 1) above is applied onto the undercoat layer of the glass plate with the undercoat layer obtained in 2) above to form a photocurable coating film. Formed. The photocurable coating film was heat-treated (prebaked) at 100 ° C. for 120 seconds with a hot plate so that the dry film thickness was 1 μm.

Subsequently, it irradiated with the exposure amount of 800 mJ / cm < ² > using the proxy exposure machine (Ushio Electric Co., Ltd. product). After exposure, the developer CD-2000 (manufactured by Fuji Film Arch Co., Ltd.) is diluted with water to a concentration of 20% by mass and developed, and the developer is washed away with ion-exchanged water. Was subjected to heat treatment at 200 ° C. for 5 minutes to obtain a test piece.

[Evaluation]
(1) Appearance observation (i) Precipitate in composition About half (about 15 ml) of the photocurable composition obtained in 1) above is poured into a cylindrical glass sample bottle having an internal volume of 30 ml, and left for 5 minutes. did. Thereafter, the glass sample bottle was turned upside down, and the inner wall of the glass sample bottle was observed with the naked eye to evaluate the adhesion state of the precipitate. At this time, a case where no precipitate was observed was evaluated as “◯”, and a case where a precipitate was observed was evaluated as “x”. The results are shown in Table 1 below.

(Ii) Uniformity of coating film The photocurable composition obtained in 1) above was applied on a soda glass substrate having a thickness of 1.1 mm under the condition of 1000 rpm using a spin coater. After coating, the coating film was dried by pre-baking on a hot plate having a surface temperature of 100 ° C. for about 2 minutes, and the surface uniformity was visually evaluated. At this time, when the presence of spotted coating unevenness, foreign matter, or repellency was not recognized on the dry coating film surface, “◯” was evaluated, and when it was recognized, “X” was evaluated.

(2) Heat resistance The test piece obtained in the above 4) was heated using a hot plate LWB-03 (manufactured by Risotech Japan Co., Ltd.) under the conditions of 200 ° C. × 1 hr. The color density (E ^* ab) before and after heating was measured using MCPD-2000 (manufactured by Otsuka Electronics Co., Ltd.), and the color difference ΔE ^* ab was calculated. The results are shown in Table 1.

(3) Light resistance A UV cut filter C-970-I (King Seisakusho Co., Ltd.) is attached to the test piece obtained in 4) above, and a super xenon fade meter SX75F (manufactured by Suga Test Instruments Co., Ltd.) is used. The light was irradiated under the condition of 2 million lx · hr. The color density (E ^* ab) before and after the light irradiation was measured using MCPD-2000 (manufactured by Otsuka Electronics Co., Ltd.), and the color difference ΔE ^* ab was calculated. The results are shown in Table 1.

[Example 2]
Example 1 1) In the preparation of the photocurable composition, the amount of ethyl lactate was changed to 768 parts, and the amount of ion-exchanged water was changed to 32 parts. A photocurable composition was prepared, a test piece was prepared, and the same evaluation was performed. The results are shown in Table 1 below.

[Example 3]
Example 1 1) In the preparation of the photocurable composition, the same procedure as in Example 1 was performed except that the addition amount of ethyl lactate was changed to 520 parts and the addition amount of ion-exchanged water was changed to 280 parts. A photocurable composition was prepared, a test piece was prepared, and the same evaluation was performed. The results are shown in Table 1 below.

[Example 4]
In the preparation of 1) photocurable composition in Example 1, a photocurable composition was prepared in the same manner as in Example 1 except that 40 parts of N, N-dimethylacetamide was added instead of ion-exchanged water. A test piece was prepared and subjected to the same evaluation. The results are shown in Table 1 below.

[Comparative Example 1]
Example 1 1) In the preparation of the photocurable composition, the amount of ethyl lactate was changed to 775 parts, and the amount of ion-exchanged water was changed to 25 parts. A photocurable composition was prepared, a test piece was prepared, and the same evaluation was performed. The results are shown in Table 1 below.
In Comparative Example 1, many foreign substances recognized as being due to the precipitation of the dye were observed in the photocurable composition, and a uniform coating film could not be formed during the test piece preparation. For this reason, stable measurement results could not be obtained, and it was not possible to evaluate heat resistance and light resistance.

[Comparative Example 2]
In the preparation of the photocurable composition in Example 1, the addition amount of ethyl lactate was changed to 450 parts, and the addition amount of ion-exchanged water was further changed to 350 parts. A photocurable composition was prepared, a test piece was prepared, and the same evaluation was performed. The results are shown in Table 1 below.
In Comparative Example 2, a large amount of coating unevenness occurred during the preparation of the test piece, and a uniform coating film could not be formed. For this reason, stable measurement results could not be obtained, and it was not possible to evaluate heat resistance and light resistance.

[Comparative Example 3]
In the preparation of 1) the photocurable composition in Example 1, test pieces were prepared and evaluated in the same manner as in Example 1 except that the photocurable composition was prepared with the following composition. The results are shown in Table 1 below.

<composition>
Solvent 800 parts Ethyl lactate Alkali-soluble resin 59 parts Benzyl methacrylate / methacrylic acid copolymer (60/40 copolymerization ratio, acid value 100 mg KOH / g average molecular weight 30,000)
・ Polymerizable monomer 88 parts Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
Photopolymerization initiator 13 parts Trichlorotriazine compound (TAZ-107: manufactured by Midori Chemical Co., Ltd.)
・ Dye 40 parts Acid red 57 (Na salt)

[Comparative Example 4]
In Example 1 1) Preparation of a photocurable composition A photocurable composition was prepared in the same manner as in Example 1 except that 40 parts of isopropyl alcohol was added instead of ion-exchanged water, and a test piece was prepared. Then, the same evaluation was performed. The results are shown in Table 1 below.

[Comparative Example 5]
Example 1 1) A photocurable composition was prepared in the same manner as in Example 1 except that 40 parts of n-butyl alcohol was added instead of ion-exchanged water in the preparation of the photocurable composition. The same evaluation was performed. The results are shown in Table 1 below.

[Comparative Example 6]
Example 1 1) A photocurable composition was prepared in the same manner as in Example 1 except that 40 parts of polyethylene glycol was added instead of ion-exchanged water in the preparation of a photocurable composition, and a test piece was prepared. Then, the same evaluation was performed. The results are shown in Table 1 below.

As shown in Table 1, in Examples 1 to 4, the occurrence of precipitates was not observed in the photocurable composition, the coating film was uniform, and the heat resistance and light resistance were not degraded by heat or light. An excellent photocurable composition could be obtained.
On the other hand, in Comparative Examples 1 and 2, a uniform coating film could not be obtained when the test piece was produced. Moreover, the comparative example 3 was remarkably inferior in heat resistance and light resistance.
In Comparative Examples 4 to 6, an organic solvent compatible with water was used instead of ion-exchanged water, but dye deposits were observed, the uniformity of the coating film was poor, and heat resistance and light resistance. A test piece capable of evaluating the property could not be obtained.

Claims (7)

  A photocurable composition comprising at least an alkali-soluble resin, a dye, a polymerizable monomer, a photopolymerization initiator, and a solvent, wherein at least one of an amide organic solvent and water is used as a constituent component. 3-30 mass% of photocurable compositions characterized by including with respect to total mass.   A photocurable composition comprising at least an alkali-soluble resin, a dye, a polymerizable monomer, a photopolymerization initiator, and a solvent, wherein the water content is 3 to 30 masses relative to the total mass of the constituent components. % Photocurable composition characterized by the above-mentioned.   The photocurable composition according to claim 1 or 2, wherein the dye is an acid dye.   The photocurable composition according to claim 1, wherein the dye contains a divalent or higher-valent metal salt.   The photocurable composition according to any one of claims 1 to 4, wherein the solvent contains an organic solvent having a boiling point of 80 ° C to 250 ° C other than the amide organic solvent.   A color filter comprising the photocurable composition according to claim 1.   A method for producing a color filter, comprising applying the photocurable composition according to any one of claims 1 to 5 on a substrate, and forming pixels on the substrate by a photolithography method.