KR20130089589A - Photosensitive colored composition, color filter, method of producing color filter, liquid crystal display device, organic electro-luminescence display device, and solid-state imaging element - Google Patents

Abstract

PURPOSE: A photosensitive coloring composition is provided to have high sensitivity and preserving stability, and the color filter using the photosensitive coloring composition is provided to have high luminance. CONSTITUTION: A photosensitive coloring composition for a color filter includes (A) hexaarylbisimidazole represented by general formula (I), (B) class 2 multi-functional thiol compound, (C) polymerizable compound, (D) propylene glycol monomethyl ether acetate soluble greater than 1 wt% at 25°C, dye of which absorption peak wavelength is 420-480 nm and (E) organic solvent. The content of the (D) dye is greater than 5 wt% for the total solid content of the photosensitive coloring composition. A color filter has a colored layer formed using the photosensitive coloring composition for color filter. A manufacturing method of the color filter includes a process of forming a colored layer by adding the photosensitive coloring composition for color filter on a support body, a process of exposure forming a latent image by exposing a pattern for the colored layer and a developing process forming a pattern by developing the colored layer having the latent image formed.

Description

PHOTOSENSITIVE COLORED COMPOSITION, COLOR FILTER, LITHOD OF PRODUCING COLOR FILTER, LIQUID CRYSTAL DISPLAY DEVICE, ORGANIC ELECTRO-LUMINESCENCE DISPLAY DEVICE, AND SOLID-STATE IMAGING ELEMENT}

This invention relates to the photosensitive coloring composition for color filters suitable for formation of the colored image which comprises the color filter used for a liquid crystal display (LCD), an organic electroluminescence display (OLED), and a solid-state image sensor (CCD, CMOS, etc.). . Moreover, this invention relates to the color filter using the said photosensitive coloring composition for color filters, the manufacturing method of a color filter, a liquid crystal display device, an organic electroluminescence display, and a solid-state image sensor.

As a method for producing a color filter for use in a liquid crystal display, an organic EL display, and a solid-state image pickup device, a dyeing method, a printing method, an electrodeposition method and a pigment dispersion method are known.

Among these, the pigment dispersion method is a method of producing a color filter by the photolithography method using a photosensitive coloring composition obtained by dispersing a pigment in various photosensitive compositions. Since the pigment is used, it has the advantage of being stable in light or heat. . Moreover, since it is patterned by the photolithographic method, it has been used widely as a preferable method for manufacturing a color filter for a large screen and a high-precision color display with high positional precision.

When manufacturing a color filter by the pigment dispersion method, a photosensitive coloring composition is apply | coated on a glass substrate with a spin coater or a roll coater, etc., and it dries to form a coating film, The colored film is formed by pattern exposure and development of the said coating film, and this By repeating the operation for each color, a color filter can be obtained.

As said pigment dispersion method, the method using the negative photosensitive coloring composition which used together the polymeric compound and the polymerization initiator in alkali-soluble resin is described (for example, Unexamined-Japanese-Patent No. 2-181704, Unexamined-Japanese-Patent No. 2). -199403, Japanese Patent Laid-Open No. 5-273411 and Japanese Patent Laid-Open No. 7-140654. Moreover, the composition which is excellent in the photocurability to which the thiol compound was added to the composition by the pigment dispersion method used for a color filter etc., and is excellent in storage stability is also proposed (for example, refer Unexamined-Japanese-Patent No. 2004-149755).

In addition, the use of a dye as a colorant is useful in that the color and luminance of the display image when the image is displayed due to the color purity of the dye itself or the vividness of the color thereof can be increased, and a technique of using the dye instead of the pigment has been proposed. (See, for example, Japanese Patent Laid-Open No. 6-75375). However, in general, a photosensitive coloring composition containing a dye has to add a large amount of dye in the photosensitive coloring composition, thereby inadequate adhesion to the substrate, insufficient curing is not obtained, or the dye is released from the exposed portion. There also arises a problem that formability is remarkably difficult.

The en-thiol polymerization system is conventionally examined as a means of improving sclerosis | hardenability (for example, refer Unexamined-Japanese-Patent No. 54-63903). However, such a polymerization system uses an active olefin or allyl ether as an ene, has a problem of poor storage stability, and has many problems in application to finer pattern formation.

Moreover, the coloring composition for color filters containing a thiol compound is proposed (for example, refer Unexamined-Japanese-Patent No. 10-253815, Unexamined-Japanese-Patent No. 3120547, and Unexamined-Japanese-Patent No. 2006-71890).

However, in the coloring composition for color filters described in JP-A-10-253815, JP-A 3120547, and JP-A-2006-71890, when a dye is used as a coloring agent, the coloring composition is high. When stored, the viscosity becomes high, resulting in poor storage stability. Moreover, when yellow dye is used especially, there exists a tendency for the fall of a sensitivity to appear remarkably. In addition, the luminance of the obtained color filter is not as high as that required, and further improvement is required.

The present invention provides a photosensitive coloring composition for color filters having high sensitivity and good storage stability. Moreover, when the color filter obtained using the said photosensitive coloring composition is produced, the photosensitive coloring composition for color filters which shows high brightness | luminance is provided. Moreover, the color filter using the said photosensitive coloring composition, its manufacturing method, and the liquid crystal display device, organic electroluminescence display, and solid-state image sensor which can display the image which have high brightness | luminance are provided.

The said subject of this invention is solved by the following means.

<1> (A) 25 degreeC to hexaaryl bisimidazole represented by following General formula (I), (B) secondary polyfunctional thiol compound, (C) polymeric compound, and (D) propylene glycol monomethyl ether acetate 1 mass% or more soluble and containing a dye having an absorption peak wavelength of 420 to 480 nm and (E) an organic solvent, the content of the dye (D) is 5% by mass or more relative to the total solids of the photosensitive coloring composition Photosensitive coloring composition for filters.

R <^1> -R <^30> respectively independently represents a chlorine atom, a hydrogen atom, or an alkoxy group in general formula (I). R ¹ to R ³⁰ The number of heavy hydrogen atoms is 22 to 29, the number of substitution of chlorine atoms is 0 to 4 and the number of substitution of alkoxy groups is 1 to 4.

<2> Photosensitive coloring composition for color filters of <1> whose said (B) secondary polyfunctional thiol compound is bivalent.

<3> The <2> above or <2>, wherein the secondary polyfunctional thiol compound (B) is ethylene glycol bis (3-mercaptobutyrate), 1,2-propylene glycol bis (3-mercaptobutyrate), The photosensitive coloring composition for color filters which is at least 1 sort (s) chosen from the group which consists of ethylene glycol bis (2-mercapto isobutyrate) and 1,2-propylene glycol bis (2-mercapto isobutyrate).

<4> Photosensitive coloring composition for color filters in any one of <1>-<3> containing (F) C.I. pigment green 58 further.

<5> The dye according to any one of <1> to <4>, wherein the dye (D) is selected from the group consisting of dyes represented by the following general formulas (II), (III) and (IV). Photosensitive coloring composition for color filters which is at least 1 sort.

In formula (II), R ⁵¹ represents an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, and an alkoxyl group having 2 to 12 carbon atoms. the carbon number of 2 to 12 alkyl group, L ⁷¹ -CO-OL ⁷² substituted-alkyl-carboxylic ^{group, L 73 -O-CO-L} 74 represented by-expressed with the alkyloxycarbonyl group, having a carbon number of 1 to 20 The phenyl group substituted by the alkyl group or the C1-C20 alkyl group substituted by the phenyl group is shown. L ⁷¹ represents an alkyl group having 2 to 12 carbon atoms, L ⁷² represents an alkylene group having 2 to 12 carbon atoms, L ⁷³ represents an alkyl group having 2 to 12 carbon atoms, and L ⁷⁴ represents an alkylene group having 2 to 12 carbon atoms. R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group or a halogen atom.

In formulas (III) and (IV), R ⁶¹ to R ⁶⁵ and R ⁷¹ to R ⁷⁴ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, and an aryl. Group or heteroaryl group.

<6> The content of hexaarylbisimidazole according to any one of <1> to <5>, in which the hexaarylbisimidazole represented by the general formula (I) is 0.1% to 10% by mass based on the solid content of the photosensitive coloring composition. Photosensitive coloring composition for color filters which is%.

<7> Photosensitive coloring for color filters in any one of <1>-<6> whose content of the said (B) secondary polyfunctional thiol compound is 0.1%-10% on a mass basis with respect to solid content of the photosensitive coloring composition. Composition.

<8> Photosensitive coloring composition for color filters in any one of <1>-<7> whose content of (D) dye is 5%-30% on a mass basis with respect to solid content of the photosensitive coloring composition.

<9> Color filter which has a colored layer formed using the photosensitive coloring composition for color filters in any one of <1>-<8>.

<10> The colored layer formation process of providing the photosensitive coloring composition for color filters in any one of <1>-<8> on a support body, and forming a colored layer, and exposing a pattern image with respect to the said colored layer, and a latent image. The manufacturing method of the color filter which has an exposure process to form, and the image development process which develops a pattern by developing the colored layer in which the said latent image was formed.

<11> Liquid crystal display device provided with the color filter as described in <9>.

<12> The organic electroluminescence display provided with the color filter as described in <9>.

<13> Solid-state image sensor provided with the color filter as described in <9>.

The photosensitive coloring composition of this invention contains the dye whose absorption peak wavelength is 420-480 nm. The dye has absorption in the yellow visible region, but under the absorption peak, the dye also absorbs exposure light such as ultraviolet rays such as i-rays or h-rays as a light source, and therefore easily inhibits photocuring of the photosensitive coloring composition. In general, dyes capture and deactivate active species generated by initiators. However, the specific hexaarylbisimidazole compound represented by the general formula (I) included in the photosensitive coloring composition of the present invention serves as an initiator, and the photosensitive coloring composition of the present invention further contains a polyfunctional thiol compound having a secondary thiol group. Since the active species generated are likely to cause chain transfer by the polyfunctional thiol compound, it is presumed that curing of the exposure area proceeds. In addition, the active species generated from the specific hexaarylbisimidazole compound represented by the general formula (I) are effectively incapable of being trapped by dyes having an absorption peak wavelength of 420 to 480 nm, and thus can effectively proceed with the reaction. Is considered. In addition, since the polyfunctional thiol compound included in the photosensitive coloring composition of the present invention is a secondary thiol group, when the photosensitive coloring composition is stored as a liquid in an unexposed state, the active species generated in the dark reaction is not subjected to the chain reaction. It is considered that there is no thickening by long-term preservation. It is considered that the photosensitive coloring composition of this invention can provide the color filter which is high in sensitivity, excellent in storage stability, and high in brightness | luminance by these interaction.

From this viewpoint, the structure of this invention which combined the secondary polyhydric thiol compound and hexaarylimidazole represented by General formula (I) with a yellow dye differs from the conventional coloring composition.

(Effects of the Invention)

According to this invention, the photosensitive coloring composition for color filters with high sensitivity and favorable storage stability can be provided. Moreover, according to this invention, when the color filter obtained using the said photosensitive coloring composition is produced, the photosensitive coloring composition for color filters which shows high luminance can be provided. Moreover, according to this invention, the color filter using the said photosensitive coloring composition and its manufacturing method can be provided, and the liquid crystal display device, organic electroluminescence display, and solid-state image sensor which can display the image which has high brightness | luminance can be provided.

Hereinafter, the photosensitive coloring composition for color filters of this invention is demonstrated in detail. In addition, below, the photosensitive coloring composition for color filters may only be called "photosensitive coloring composition" or "coloring composition."

In the present specification, the symbol &quot; ~ &quot; indicates the range of the lower limit value to the upper limit value. In addition, in the description of group in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent.

The photosensitive coloring composition for color filters of this invention is (A) hexaarylbisimidazole represented by general formula (I), (B) secondary polyfunctional thiol compound, (C) polymeric compound, (D) propylene glycol mono 1 mass% or more of soluble at 25 degreeC, and the absorption peak wavelength of 420-480 nm are contained in methyl ether acetate (henceforth "(D) dye" suitably), and (E) organic solvent is contained, The said (D The content of dye is 5 mass% or more with respect to the total solid of the photosensitive coloring composition.

The essential components (A)-(D) and arbitrary components which are contained in the photosensitive coloring composition for color filters of this invention are demonstrated below.

(A) Hexaarylbisimidazole represented by general formula (I)

The photosensitive coloring composition of this invention contains at least 1 sort (s) hexaarylbisimidazole represented by following General formula (I). The hexaarylbisimidazole represented by (A) general formula (I) in the photosensitive coloring composition of this invention acts as a photoinitiator or a thermal polymerization initiator. Therefore, in the colored layer which provided and formed the photosensitive coloring composition on a board | substrate, (C) polymeric compound superposes | polymerizes by exposing through an exposure mask etc., and the said colored layer hardens | cures and a pattern is formed.

The photosensitive coloring composition of the present invention contains the hexaarylbisimidazole represented by the general formula (I), but the reason is not clear, but (D) of the colored layer under coexistence with a yellow dye having an absorption peak wavelength of 420 to 480 nm. The exposure sensitivity can be effectively improved.

R <^1> -R <^30> respectively independently represents a chlorine atom, a hydrogen atom, or an alkoxy group in general formula (I). The number of hydrogen atoms in R ¹ to R ³⁰ is ²² to ²⁹ , the number of substitution of chlorine atoms is 0 to 4 and the number of substitution of alkoxy groups is 1 to 4.

Examples of the alkoxy group represented by R ¹ to R ³⁰ in hexaarylbisimidazole represented by the general formula (I) include alkoxy groups having 1 to 4 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, and a propoxy. A timing, an isopropoxy group, a butoxy group, an isobutoxy group, etc. are mentioned. It is preferable that the alkoxy group which R <^1> -R <^30> represents is a C1-C2 alkoxy group, and a methoxy group or an ethoxy group is especially preferable from a viewpoint of the solubility to a solvent.

R ¹ to R ³⁰ each independently represent any one of a chlorine atom, a hydrogen atom or an alkoxy group, but from the viewpoint of reactivity and transparency, the number of hydrogen atoms in R ¹ to R ³⁰ is 22 to 27, and the substitution of chlorine atoms It is preferable that the number is 1-4 and the substitution number of an alkoxy group is 2-4, and this embodiment is employ | adopted in this embodiment.

The specific example of hexaarylbisimidazole represented by general formula (I) is shown below. However, the present invention is not limited thereto.

Among these, (I-1), (I-2), (I-4), and (I-11) are preferable from the viewpoint of solubility, reactivity, and transparency in a solvent.

The content of the hexaarylbisimidazole compound represented by General Formula (I) in the present invention is preferably 0.1% to 10% by mass based on the solids content of the photosensitive coloring composition, from the viewpoint of reactivity and preservation, and is preferably 1%. It is more preferable that it is-7%.

In this specification, "solid content of the photosensitive coloring composition" means the sum total of the component except the organic solvent from the all components which comprise the photosensitive coloring composition.

Although hexaarylbisimidazole represented by general formula (I) in this invention mainly acts as an initiator which initiates superposition | polymerization of (C) polymeric compound, in this invention, hexaaryl bisimid represented by general formula (I) The polymerization initiator of structures other than a dozol can be used together. The polymerization initiator of a structure different from hexaarylbisimidazole represented by general formula (I) is mentioned later.

(B) secondary polyfunctional thiol compounds

The photosensitive coloring composition of this invention contains the (B) secondary polyfunctional thiol compound.

The secondary polyfunctional thiol compound (B) in the present invention may contain two or more secondary thiol groups in a molecule, and does not have a primary thiol group.

In this invention, the sensitivity of a photosensitive coloring composition improves by including (B) the secondary polyfunctional thiol compound, and the preservation property of the photosensitive coloring composition can be kept stable.

As the (B) secondary polyfunctional thiol compound in the present invention, an aliphatic or aromatic secondary polyfunctional thiol compound can be used, but an aliphatic secondary polyfunctional thiol compound is preferable. Moreover, for the reason similar to the above, as a (B) secondary polyfunctional thiol compound in this invention, the bivalent secondary polyfunctional thiol compound whose number of secondary thiol groups contained in a molecule | numerator is two is preferable.

Specific examples of the (B) secondary polyfunctional thiol compound in the present invention include ethylene glycol bis (3-mercaptobutyrate), 1,2-propylene glycol bis (3-mercaptobutyrate), and diethylene glycol bis (3- Mercaptobutyrate), butanediolbis (3-mercaptobutyrate), octanediolbis (3-mercaptobutyrate), trimethylolpropanetris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), Dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropioate Nate), butanediolbis (2-mercaptopropionate), octanediolbis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mer) Topropionate), dipentaerythritol hexakis (2-mercaptopropionate), ethylene glycol bis (3-mercaptoisobutyrate), 1,2-propylene glycol bis (3-mercaptoisobutyrate) , Diethylene glycol bis (3-mercaptoisobutyrate), butanediolbis (3-mercaptoisobutyrate), octanediolbis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoi Sobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexakis (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1,2- Propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediolbis (2-mercaptoisobutyrate), octanediolbis (2-mercaptoisobutyrate) ), Trimethylolpropane tris (2-mercapto Sobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), ethylene glycol bis (4-mercapto valerate), 1,2-propylene Glycolbis (4-mercaptoisovalate), Diethylene glycol bis (4-mercapto valerate), Butanediol bis (4-mercapto valerate), Octanediol bis (4- mercapto valerate), Trimethyl Roll propane tris (4-mercapto valerate), pentaerythritol tetrakis (4-mercapto valerate), dipentaerythritol hexakis (4- mercapto valerate), ethylene glycol bis (3- mercapto valerate) , 1,2-propylene glycol bis (3-mercapto valerate), diethylene glycol bis (3- mercapto valerate), butanediol bis (3- mercapto valerate), octane diol bis (3- mercapto valerate Trimethylolpropane tris (3-mercaptobal) Aliphatic secondary polyfunctional thiol compounds such as lerate), pentaerythritol tetrakis (3-mercapto valerate) and dipentaerythritol hexakis (3-mercapto valerate).

Examples of the aromatic secondary polyfunctional thiol compound include phthalic acid di (1-mercaptoethyl ester), phthalic acid di (2-mercaptopropyl ester), phthalic acid di (3-mercaptobutyl ester), and phthalic acid di (3-mercaptoyl) Sobutyl ester) etc. are mentioned.

Among these exemplified secondary polyfunctional thiol compounds, ethylene glycol bis (3-mercaptobutyrate), 1,2-propylene glycol bis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptoisobutyrate) or 1,2-propylene glycol bis (2-mercaptoisobutyrate) is particularly preferred.

Although the photosensitive coloring composition of this invention should just contain 1 type of secondary polyfunctional thiol compound, you may use 2 or more types together.

The content of the secondary polyfunctional thiol compound in the photosensitive coloring composition of the present invention is preferably 0.1% to 10% by mass based on the solids content of the photosensitive coloring composition, from the viewpoints of reactivity and storage properties, and is 0.5% to 7%. It is more preferable.

(C) a polymerizable compound

The photosensitive coloring composition of this invention contains at least 1 sort (s) polymeric compound. (C) As a polymeric compound, the addition polymeric compound which has at least 1 ethylenically unsaturated double bond is mentioned, for example.

Specifically, the (C) polymerizable compound is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such compound groups are widely known in the above industrial fields, and in the present invention, these can be used without particular limitation. These may be, for example, any of chemical forms such as monomers, prepolymers (ie dimers, trimers and oligomers) or mixtures thereof and their (co) polymers.

Examples of monomers and their (co) polymers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides of unsaturated carboxylic acids, and These (co) polymers are mentioned. Preferred examples include esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds and amides of unsaturated carboxylic acids and aliphatic polyamine compounds and their (co) polymers. Moreover, addition reaction product of unsaturated carboxylic ester or amide which has nucleophilic substituent, such as a hydroxyl group, an amino group, or a mercapto group, and monofunctional or polyfunctional isocyanate or epoxy; And dehydration condensation reaction products of the above unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional carboxylic acids are also preferably used. Furthermore, addition reaction products of unsaturated carboxylic esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines or thiols; And a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving group such as a halogen group or a tosyloxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol. As another example, it is also possible to use a compound group obtained by replacing the unsaturated carboxylic acid with unsaturated phosphonic acid, styrene or vinyl ether.

Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, and propylene glycol diacryl. Latene, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol di Acrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate Site, there may be mentioned acrylic acid esters such as sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and isocyanuric acid EO modified triacrylate.

Moreover, as a specific example of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, Trimethylol ethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetrametha Acrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl ] Dimethylmethane and meta, such as bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane Crylic acid ester is mentioned.

Moreover, as an example of the monomer of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1, 3- butanediol diitaconate, 1, 4- butanediol diitaconate Itaconic acid ester, such as tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetraitaconate; For example, Crotonic acid ester, such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate; For example, isocrotonic acid ester, such as ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate; For example, maleic ester, such as ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramalate, is mentioned.

As monomers of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids, for example, aliphatic alcohol esters and Japanese Patent Laid-Open Nos. 59-5240 described in JP-A-51-47334 and JP-A-57-196231. Others such as those having an aromatic skeleton described in Japanese Patent Application Laid-Open No. 59-5241, Japanese Patent Laid-Open No. 2-226149, and containing an amino group described in Japanese Patent Laid-Open No. 1-165613 Esters are also preferably used. In addition, the above-mentioned ester monomer can be used also as a mixture.

Moreover, as an example of the monomer of the amide of an aliphatic polyhydric amine compound and an unsaturated carboxylic acid, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylenebis- acrylamide, 1, 6- hexamethylene bis- Methacrylamide, diethylene triamine trisacrylamide, xylene bis acrylamide, xylene bis methacrylamide, and the like.

Examples of other preferred amide monomers include those having a cyclohexylene structure described in Japanese Patent Publication No. 54-21726.

Moreover, as a (C) polymeric compound, the urethane type addition polymeric compound manufactured using addition reaction of an isocyanate and a hydroxyl group is also preferable. As a specific example of such a urethane type addition polymeric compound, the vinyl monomer containing a hydroxyl group represented by the following general formula is added to the polyisocyanate compound which has two or more isocyanate groups in 1 molecule as described in Unexamined-Japanese-Patent No. 48-41708, for example. And vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule obtained.

CH ₂ = C (R) COOCH ² CH (R ') OH

[Wherein R and R ′ each independently represent H or CH ₃ ]

About these polymeric compounds, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of the photosensitive coloring composition. For example, a structure with many unsaturated group content per molecule is preferable from a viewpoint of a sensitivity, and in many cases, bifunctional or more is preferable. Moreover, a trifunctional or more thing is good from a viewpoint of raising the intensity | strength of the photosensitive colored cured film. Moreover, the method of adjusting both a sensitivity and a strength by using together the thing of another functional water and / or another polymerizable group (for example, an acrylic acid ester, a methacrylic acid ester, a styrene type compound, a vinyl ether type compound) is also effective. In addition, the selection and use of the polymerizable compound are important factors also in terms of compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (dye, pigment), binder polymer, etc.) contained in the photosensitive coloring composition. For example, the compatibility can be improved by using a low-purity compound or using 2 or more types together. Moreover, the polymeric compound which has a specific structure can also be selected from a viewpoint of improving adhesiveness with hard surfaces, such as a support body.

Content (polymer content in the case of 2 or more types) of the polymeric compound in the total solid of the photosensitive coloring composition does not have limitation in particular, 10 mass%-80 mass% are preferable from a viewpoint which acquires the effect of this invention more effectively, 15 mass%-75 mass% are more preferable, and 20 mass%-60 mass% are especially preferable.

(D) 1 mass% or more soluble in propylene glycol monomethyl ether acetate, and absorption peak wavelength is 420-480 nm.

The photosensitive coloring composition of this invention contains at least 1 sort (s) of dye ((D)) which is 1 mass% or more soluble at 25 degreeC, and has an absorption peak wavelength of 420-480 nm in (D) propylene glycol monomethyl ether acetate. .

The dye (D) is yellow, and the photosensitive coloring composition of this invention is colored by including (D) dye. The photosensitive coloring composition of this invention may contain coloring agents other than (D) dye as a coloring agent. Although coloring agents other than (D) dye are mentioned later, the photosensitive coloring composition of this invention is colored green, red, and other colors by containing coloring agents other than (D) dye, such as C.I.Pigment Green 58.

The dye (D) of the present invention needs to be dissolved in propylene glycol monomethyl ether acetate at 1% by mass or more at 25 ° C.

In addition, the dye (D) of the present invention requires the absorption peak wavelength to be 420 to 480 nm. The absorption peak wavelength of the dye in the present invention is determined by dissolving the dye in propylene glycol monomethyl ether acetate and measuring it with an absorbance meter (UV-1800PC manufactured by Shimadzu).

The dye (D) of the present invention may be a dye having any structure as long as it is soluble in propylene glycol monomethyl ether acetate at 25 ° C of 1% by mass or more and has an absorption peak wavelength of 420 to 480 nm.

In particular, the dye (D) is selected from the group consisting of dyes represented by the following general formula (II), general formula (III), general formula (IV), general formula (X-1) and general formula (X-2). It is preferable that it is at least 1 sort (s).

First, the dye represented by general formula (II) is demonstrated.

In formula (II), R ⁵¹ represents an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, and an alkoxyl group having 2 to 12 carbon atoms. the carbon number of 2 to 12 alkyl group, L ⁷¹ -CO-OL ⁷² substituted-alkyl-carboxylic ^{group, L 73 -O-CO-L} 74 represented by-expressed with the alkyloxycarbonyl group, having a carbon number of 1 to 20 The phenyl group substituted by the alkyl group or the C1-C20 alkyl group substituted by the phenyl group is shown. L ⁷¹ represents an alkyl group having 2 to 12 carbon atoms, L ⁷² represents an alkylene group having 2 to 12 carbon atoms, L ⁷³ represents an alkyl group having 2 to 12 carbon atoms, and L ⁷⁴ represents an alkylene group having 2 to 12 carbon atoms. R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group or a halogen atom.

Examples of the alkyl group having 2 to 20 carbon atoms represented by R ^{51 in} General Formula (II) include an ethyl group, n-propyl group, isopropyl group, n-hexyl group, n-nonyl group, n-decyl group, n-dodecyl group and 2- Ethyl hexyl group, 1, 3- dimethyl butyl group, 1-methyl butyl group, 1, 5- dimethylhexyl group, 1, 1, 3, 3- tetramethyl butyl group etc. are mentioned.

Cyclohexylethyl group, 3-cyclohexylpropyl group, 8-cyclohexyl octyl group, etc. are mentioned as a C2-C12 cyclohexyl alkyl group of the alkyl chain which R <^51> represents.

Examples of the alkylcyclohexyl group having 1 to 4 carbon atoms of the alkyl chain represented by R ⁵¹ include 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2- (n-butyl) cyclohexyl group, and the like.

As a C2-C12 alkyl group substituted by the C2-C12 alkoxyl group which R <^51> represents, 3-ethoxy-n-propyl group, a propoxypropyl group, 4-propoxy-n-butyl group, 3-methyl- n-hexyloxyethyl group, 3- (2-ethylhexyloxy) propyl group, etc. are mentioned.

An o-isopropylphenyl group etc. are mentioned as a phenyl group substituted by the C1-C20 alkyl group which R <^51> represents.

Examples of the alkyl group having 1 to 20 carbon atoms substituted with a phenyl group represented by R ⁵¹ include a DL-1-phenylethyl group, a benzyl group, and a 3-phenyl-n-butyl group.

Examples of the alkyl group having 2 to 12 carbon atoms in L ⁷¹ and L ⁷³ include ethyl group, propyl group, n-hexyl group, n-nonyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, 1,3- Dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group, etc. are mentioned.

Examples 2 to 12 carbon atoms of the alkylene group in L ⁷² and L ^74, and the like dimethylene group and hexamethylene group.

As R ⁵² to R ⁵⁵ , a hydrogen atom, a methyl group, an ethyl group, n-propyl group, n-butyl group, isopropyl group, sec-butyl group, tert-butyl group, carboxyl group, fluorine atom, chlorine atom, bromine atom and iodine atom Etc. are mentioned, Preferably they are a hydrogen atom, a methyl group, an ethyl group, n-propyl group, n-butyl group, isopropyl group, sec-butyl group, tert- butyl group, a fluorine atom, or a chlorine atom.

The following compound etc. are mentioned as a specific example of a compound represented by the said General formula (II).

Next, the dye represented by general formula (III) or general formula (IV) is demonstrated.

In formulas (III) and (IV), R ⁶¹ to R ⁶⁵ and R ⁷¹ to R ⁷⁴ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, and an aryl. Group or heteroaryl group.

The preferable substituent in the compound represented by general formula (III) or general formula (IV) is demonstrated.

Examples of the alkyl group in the case where R ⁶¹ to R ⁶⁵ or R ⁷¹ to R ⁷⁴ represent an alkyl group include an alkyl group having 1 to 48 carbon atoms (more preferably, 1 to 18 carbon atoms). An alkyl group may be sufficient. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group and cyclopropyl group , Cyclopentyl group, cyclohexyl group, 1-norbornyl group and 1-adamantyl group, and the like, and preferably, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, Hexyl group, heptyl group, octyl group or 2-ethylhexyl group.

Examples of the alkoxy group in the case where R ⁶¹ to R ⁶⁵ or R ⁷¹ to R ⁷⁴ represent an alkoxy group include an alkoxy group having 1 to 48 carbon atoms (more preferably 1 to 12 carbon atoms). Specific examples thereof include methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxy group, dodecyloxy group and cycloalkyloxy group (e.g. cyclopentyloxy group and cyclohexyl oxy). Season, etc.) etc., Preferably, they are a methoxy group, an ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, or t-butoxy group.

Examples of the alkoxycarbonyl group in the case where R ⁶¹ to R ⁶⁵ or R ⁷¹ to R ⁷⁴ represent an alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 48 carbon atoms (more preferably 2 to 12 carbon atoms). Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, and the like, and preferably a methoxycarbonyl group or an ethoxycarbonyl group.

Examples of carbamoyl groups in the case where R ⁶¹ to R ⁶⁵ or R ⁷¹ to R ⁷⁴ represent carbamoyl groups include carbamoyl groups having 1 to 48 carbon atoms (more preferably 1 to 12 carbon atoms). Specific examples thereof include carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, and N-phenylcarbamo Diary, N-methylN-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group, and the like, and preferably N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamo Diary, N-propylcarbamoyl group or N-phenylcarbamoyl group.

Examples of the sulfamoyl group in the case where R ⁶¹ to R ⁶⁵ or R ⁷¹ to R ⁷⁴ represent sulfamoyl groups include sulfamoyl groups having 32 or less carbon atoms (more preferably, 16 or less carbon atoms). Specific examples thereof include sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-hexylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group and N-cyclohexyl sulfamoyl group etc. are mentioned, Preferably, they are N-ethyl-N-hexyl sulfamoyl group, N-ethyl-N-phenyl sulfamoyl group, or N-cyclohexyl sulfamoyl group.

Examples of the aryl group in the case where R ⁶¹ to R ⁶⁵ or R ⁷¹ to R ⁷⁴ represent an aryl group include an aryl group having 6 to 48 carbon atoms (more preferably 6 to 12 carbon atoms). As the specific example, a phenyl group, a naphthyl group, etc. are mentioned, Preferably it is a phenyl group.

Examples of the heteroaryl group in the case where R ⁶¹ to R ⁶⁵ or R ⁷¹ to R ⁷⁴ represent a heteroaryl group include a heteroaryl group having 1 to 32 carbon atoms (more preferably 1 to 12 carbon atoms). Specific examples thereof include 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group and benzo Triazol-1-yl group etc. are mentioned, Preferably, they are 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, or a benzotriazol-1-yl group.

R ⁶² and R ⁷¹ are each independently an alkyl group having 1 to 8 carbon atoms having a substituent, an aryl group having 6 to 12 carbon atoms or a cyano group having a substituent, and more preferably a methyl group, an ethyl group, an isopropyl group, and t- It is a butyl group, a phenyl group, or o-methylphenyl group.

R ⁷³ is preferably a hydrogen atom. R ⁶¹ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R ⁶⁴ , R ⁶⁵ , R ⁷² and R ⁷³ are not particularly limited in structure, but alkoxycarbonyl group or carbamo having a substituted alkyl group, PEO (polyethylene glycol) chain, PPO (polypropylene glycol) chain, ammonium salt or polymerizable group in its structure It is preferable that it is a diary or a sulfamoyl group, More preferably, it is a sulfamoyl group.

As for the compound represented by general formula (III) or general formula (IV), it is more preferable that it is a compound represented with the following general formula (V) or general formula (VI).

In the general formula (Ⅴ) and formula ^{(Ⅵ) R 61 ~R 63,} R 71, R 73 and R ⁷⁴ are in the formula (Ⅲ), formula ^{(Ⅳ) R 61 ~R 63,} R 71, It is synonymous with R ⁷³ and R ⁷⁴ , respectively. R ⁶⁷ , R ⁶⁹ , R ⁷⁶ and R ⁷⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 48 carbon atoms, and R ⁶⁶ , R ⁶⁸ , R ⁷⁵ and R ⁷⁷ each independently represent an alkyl group having 1 to 48 carbon atoms and carbon number It represents a 6-48 aryl group or a C1-C32 heteroaryl group.

The preferable substituent in the compound represented by general formula (V) or general formula (VI) is demonstrated.

^{R 61 ~R 63, R 71,} R 73 and R ⁷⁴ in the concrete examples and the preferable range in the formula (Ⅲ) and formula ^{(Ⅳ) R 61 ~R 63,} R 71, R 73 and R ⁷⁴ It is the same as the specific example and preferable range shown by each.

The alkyl group represented by R ⁶⁷ , R ⁶⁹ , R ⁷⁶ or R ⁷⁸ is synonymous with the alkyl group represented by R ⁶¹ to R ⁶⁸ , R ⁷¹ to R ⁷⁴ in General Formulas (III) and (IV), and specific examples thereof and Preferred ranges are also the same. In addition, specific examples of the alkyl group represented by R ⁶⁶ , R ⁶⁸ , R ⁷⁵ or R ⁷⁷ and the preferred ranges thereof include R ⁶¹ to R ⁶⁸ , R ⁷¹ to R ⁷⁴ in General Formula (III) and General Formula (IV). It is the same as the specific example of the alkyl group shown and its preferable range, respectively.

Specific examples and preferred ranges in the aryl group represented by R ⁶⁶ , R ⁶⁸ , R ^75, or R ⁷⁷ are represented by R ⁶¹ to R ⁶⁸ , R ⁷¹ to R ⁷⁴ in General Formula (III) and General Formula (IV). The same is true for each aryl group.

Specific examples of the heteroaryl group represented by R ⁶⁶ , R ⁶⁸ , R ⁷⁵ or R ⁷⁷ and the preferred ranges thereof include R ⁶¹ to R ⁶⁸ , R ⁷¹ to R ⁷⁴ in General Formula (III) and (IV). It is the same as the specific example of the heteroaryl group shown, and its preferable range, respectively.

Among these, as R ⁶¹ to R ⁶³ , R ⁷¹ , R ⁷³ and R ^74, each independently a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a phenyl group or an o-methylphenyl group is particularly preferable, and R ⁶⁶ , R ⁶⁸ , R ^{As 75} and R ⁷⁷ , N-ethyl-N-hexylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group or N-cyclohexylsulfamoyl group are each independently preferable.

The particularly preferable substituent of the dye represented by general formula (V) or general formula (VI) is demonstrated. As R ⁷⁶ and R ^78, hydrogen atoms are preferable, respectively. As R ⁶⁶ , R ⁶⁸ , R ⁷⁵ and R ⁷⁷ , a structure having a substituted alkyl group, a PEO (polyethylene glycol) chain, a PPO (polypropylene glycol) chain, an ammonium salt or a polymerizable group is preferable, and more preferably 2 to 2 carbon atoms. It is preferable that it is an alkyl group of 8 or has a methacrylic acid group on an alkyl chain.

Next, the specific example of dye represented by general formula (III) or general formula (IV) is shown below. However, the present invention is not limited thereto.

Next, the dye represented by general formula (VII-1) or general formula (VII-2) is demonstrated.

R ⁸¹ and R ⁸² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, -COOR ⁸³ or -CONR ⁸³ R ⁸⁴ in formula (VII-1) and formula (VII-2). R ⁸⁵ , R ⁸⁶ and R ⁸⁷ each independently represent a hydrogen atom, an alkyl group or an aryl group. Two of R ⁸⁵ , R ^86, and R ^{87 may} be bonded to each other to form a 5-membered ring, a 6-membered ring, or a 7-membered ring. R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or an alkyl group. Ar represents an aromatic ring or a saturated heterocycle. n and m each independently represent 0, 1 or 2; R ⁸¹ to R ⁸⁴ and Ar each do not have a dissociable group. At least one of R ⁸¹ , R ^82, and Ar has an alkyl group having 6 to 30 carbon atoms.

The alkyl group represented by R ⁸¹ or R ⁸² in the general formulas (X-1) and (X-2) may have a substituent, and an alkyl group having 1 to 30 carbon atoms is preferable. Specifically, for example, methyl group, ethyl group, i-propyl group, normal butyl group, third butyl group, 1-methylcyclopropyl group, normal hexyl group, 3-heptyl group, normal octyl group, 2-ethylhexyl group, A normal nonyl group, a normal undecyl group, a chloromethyl group, a trifluoromethyl group, an ethoxycarbonylmethyl group, a perfluoroalkyl group (for example, a perfluoromethyl group etc.) etc. are preferable. Especially, a C6-C30 alkyl group is preferable, and a normal hexyl group, a normal octyl group, 2-ethylhexyl group, 2-methylhexyl group, etc. are preferable specifically ,.

The alkoxy group represented by R ⁸¹ or R ⁸² may have a substituent, and an alkoxy group having 1 to 30 carbon atoms is preferable. Specifically, for example, methoxy group, ethoxy group, normal butoxy group, third butoxy group, 3-heptyloxy group, normal nonyloxy group, normal undecyloxy group, chloromethyloxy group, trifluoromethoxy group, ethoxy Carbonylmethoxy group, perfluoroalkyloxy group (for example, perfluoromethoxy group etc.) etc. are preferable. In particular, a methoxy group and an ethoxy group are preferable.

The aryl group represented by R ⁸¹ or R ⁸² may have a substituent, and an aryl group having 6 to 36 carbon atoms is preferable. Specifically, for example, a phenyl group, a 2,6-dimethylphenyl group, a 4-methoxyphenyl group, a 4-dibutylaminophenyl group, a 4- (2-ethylhexyloxy) phenyl group, a 4-hexylphenyl group, and the like are preferable.

The alkyl group represented by R ⁸¹ or R ⁸² in the general formulas (X-1) and (X-2) may have a substituent, and an alkyl group having 1 to 30 carbon atoms is preferable. Specifically, for example, methyl group, ethyl group, ethoxycarbonylmethyl group, normal hexyl group, normal octyl group, 2-ethylhexyl group, dodecyl group, cyclohexyl group, cyanoethyl group, 2,2,3,3-tetra Fluoropropyl group, chloroethyl group, acetoxyethyl group and dimethylaminomethyl group are preferable.

The aryl group represented by R ⁸¹ or R ⁸² may have a substituent, and an aryl group having 6 to 36 carbon atoms is preferable. Specifically, for example, a phenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-methoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group and 4-dodecyloxyphenyl group are preferable. The 5-, 6-, and 7-membered rings formed by R ⁸⁵ and R ⁸⁶ bonding to each other are 5-, 6-, and 7-membered rings containing nitrogen atoms, pyrrolidine rings, piperidine rings, morpholine rings, and piperazine rings. And hexamethyleneimine ring is preferable. These 5-membered rings, 6-membered rings, and 7-membered rings may further have a substituent.

As the aromatic ring and saturated heterocyclic ring represented by Ar in General Formula (X-2), a 5- or 6-membered ring is preferable. Specifically, a benzene ring, naphthalene ring, pyrrole ring, indole ring, pyridine ring, quinoline ring, pyrazine ring, quinoxaline ring, thiazole ring, thiazolin ring, oxazole ring, oxazoline ring, imidazole ring and imidazoline ring Saturated heterocycles, such as an aromatic ring, a pyrrolidine ring, a tetrahydrofuran ring, and a tetrahydrothiophene ring, are preferable, and a benzene ring, a pyrrole ring, and an indole ring are especially preferable.

The aromatic ring and saturated heterocycle represented by Ar may be unsubstituted or may be substituted. When Ar is substituted, the substituent can be suitably selected from the substituents except a dissociative group. Specific examples thereof include an alkyl group, an alkoxy group, an aryl group, and a substituted amino group.

The said alkyl group, an alkoxy group, and an aryl group are synonymous with the alkyl group, the alkoxy group, and the aryl group in said R <^81> and R <^82> , and their preferable embodiment is also the same.

As said substituted amino group, an alkylamino group is preferable, and the alkylamino group which has 6-30 carbon atoms (preferably 7-20) of an alkyl site is more preferable.

Especially, when Ar is substituted, the substituent is preferably an alkyl group, an alkylamino group having 6 to 30 carbon atoms (preferably 7 to 20) and an alkoxy group.

R ⁸¹ to R ⁸⁴ and Ar both do not have a dissociable group (does not contain NH).

R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or an alkyl group. Examples of the alkyl group represented by R ⁸³ and R ⁸⁴ include an alkyl group having 1 to 10 carbon atoms. As a specific example, a methyl group, an ethyl group, a propyl group, a butyl group, and 2-ethylhexyl group are mentioned. R ⁸³ and R ⁸⁴ are preferably hydrogen atoms.

n and m each independently represent 0, 1 or 2; Preferably it is 0 or 1.

At least one of R ⁸¹ , R ^82, and Ar has an alkyl group having 6 to 30 carbon atoms. Preferably, R ⁸² is an alkyl group of 6 to 30 carbon atoms or Ar has an alkyl group of 6 to 30 carbon atoms. It is also a preferred embodiment that Ar has an alkylamino group having 6 to 30 carbon atoms in the alkyl moiety as a substituent.

The specific example of the pyrazolone type methine pigment | dye represented by the said General formula (VII-1) and General formula (VII-2) is shown below. The present invention is not limited by these embodiments.

In the following structure, "Me" represents a methyl group, "Et" represents an ethyl group, "n-Pr" represents a normal propyl group, "i-Pr" represents an isopropyl group, "n-Bu" and "Bu" represents a normal butyl group, "t-Bu" represents a tert-butyl group, and "Ph" represents a phenyl group. Further, "C ₈ H _17" in the D-13 represents an n-octyl.

"ET1" in the compound D-5 and "ET2" in the compound D-9 are groups shown below, respectively. The dashed lines in ET1 and ET2 indicate the position of the bond.

Pyrazolone methine pigment | dye which has a C6-C30 alkyl group in a molecule | numerator is the method of Unexamined-Japanese-Patent No. 2008-248123, Unexamined-Japanese-Patent No. 2-3450, and Unexamined-Japanese-Patent No. 49-114420. You can get it.

In addition, pyrazolone methine pigment | dye is manufactured also by the well-known synthetic | combination method shown to each publication of Unexamined-Japanese-Patent No. 2707371, Unexamined-Japanese-Patent No. 5-45789, Unexamined-Japanese-Patent No. 2009-263517, and Unexamined-Japanese-Patent No. 3-72340. can do.

Although the above-mentioned preferred dye (D) has been described, in addition, for example, phthalocyanine-based dyes (for example, phthalocyanine compounds described in US Patent 2008/0076044 A1 specification), xanthene-based dyes, triarylmethane-based dyes, methine-based dyes, Dipyrromethene-based dyes (e.g., JP-A-2008-292970); and the like, are soluble in propylene glycol monomethyl ether acetate at 1% by mass or more at 25 ° C, and the absorption peak wavelength is 420 to 480 nm. If it is a phosphorus dye, it can be used as (D) dye in this invention.

The photosensitive coloring composition of this invention may contain 1 type of (D) dye, and may contain 2 or more types.

Moreover, it is also possible to use the dye which does not exist in the range whose absorption peak wavelength is 420-480 nm together with (D) dye.

Content (D) of the (D) dye in the total solid of the photosensitive coloring composition is 5 mass% or more from a viewpoint of containing at least fixed so that a sensitizing dye may not be contained as (D) dye, and is high transparency 5 mass%-30 mass% are preferable from a viewpoint of that, and 5 mass%-15 mass% are more preferable.

Pigment

Moreover, a pigment can also be used for the photosensitive coloring composition of this invention with the said (D) dye as a coloring agent.

Such pigments include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, ananthrone, benzimidazolone, gisazzo condensation, gisazo, azo, indanthrone, phthalocyanine, triarylcarbonium, diox Photo, aminoanthraquinone, diketopyrrolopyrrole, indigo, thioindigo, isoindolin, isoindolinone, pyrantrone, isobioanthrone and the like.

More specifically, as the pigment, for example, perylene pigments such as Pigment Red 190, Pigment Red 224, Pigment Violet 29, Perinone pigments such as Pigment Orange 43 or Pigment Red 194, Pig Quinaclidone pigments, such as pigment violet 19, pigment violet 42, pigment red 122, pigment red 192, pigment red 202, pigment red 207 or pigment red 209 Quinacridonequinone pigments such as red 206, pigment orange 48 or pigment orange 49, anthraquinone pigments such as pigment yellow 147, anthrone pigments such as pigment red 168, pigment brown 25 Benzimidazolon pigments, such as pigment violet 32, pigment orange 36, pigment yellow 120, pigment yellow 180, pigment yellow 181, pigment orange 62, or pigment red 185, Pigment yellow 93, pig Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment JS-A condensed pigments such as red 166, pigment red 220, pigment red 221, pigment red 242, pigment red 248, pigment red 262 or pigment brown 23, pigment yellow 13 Pigment yellow pigments such as Pigment Yellow 83 or Pigment Yellow 188, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Azo pigments such as red 53, pigment orange 64 or pigment red 247, indanthrone pigments such as pigment blue 60, pigment green 7, pigment green 36, pigment green 37, pig Green 58, pigment blue 16, pigment blue 75 or pigment blue Triarylcarbonium pigments, such as phthalocyanine pigments, such as 15, pigment blue 56, or pigment blue 61, dioxazine pigments, such as pigment violet 23 or pigment violet 37, and amino, such as pigment red 177 Diketopyrrolopyrrole pigments, such as an anthraquinone pigment, pigment red 254, pigment red 255, pigment red 264, pigment red 272, pigment orange 71 or pigment orange 73 Isoindolin pigments such as thioindigo pigments such as red 88, isoindolin pigments such as pigment yellow 139, pigment orange 66, pigment yellow 109 or pigment orange 61, pigment orange 40 Or pyrantrone pigments, such as pigment red 216, and isobioanthrone pigments, such as pigment violet 31, are mentioned.

Pigment green 36 and pigment green 58 are preferable among these pigments from a viewpoint of obtaining a preferable color, and pigment green 58 ((F) C.I. Pigment green 58) is more preferable.

When using a pigment for the photosensitive coloring composition of this invention, it is especially preferable that it is a pigment of microparticles | fine-particles. As particle size of a pigment, it is preferable that average primary particle diameters are 10 nm-200 nm, and it is more preferable that they are 10 nm-100 nm.

Moreover, before preparing a photosensitive coloring composition, it is preferable to mix a pigment particle previously with a dispersing agent, an organic solvent, etc., and to fully disperse, and to prepare a photosensitive coloring composition as a pigment dispersion liquid.

(E) Organic solvents

The photosensitive coloring composition of this invention can contain at least 1 sort (s) of organic solvents.

The organic solvent (E) is not particularly limited as long as the organic solvent can satisfy the solubility of each component and the coating composition when used as a colored composition, and in particular, the organic solvent is selected in consideration of the solubility, coating property and safety of a dye or a binder. It is preferable.

(E) As the organic solvent, ethyl acetate, acetic acid-n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, oxy Acetic acid alkyl esters (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically methyl methoxyacetate, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, etc.) may be mentioned. ), 3-oxypropionic acid alkyl esters (e.g., 3-oxypropionate methyl, 3-oxypropionate ethyl, etc. (specifically, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl) , Ethyl 3-ethoxypropionate, etc.), 2-oxypropionic acid alkyl esters (e.g., 2-oxypropionic acid Methyl, 2-oxypropionate, propyl 2-oxypropionate, and the like (specifically, 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionic acid propyl, 2-ethoxypropionate methyl, 2-ethoxy Ethyl propionate, etc.)), methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate (specifically methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2) Ethyl methyl propionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetic acid, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, cyclohexyl acetate and 1-methyl propionate Ester, such as 2-methoxy ethyl, is mentioned.

(E) As the organic solvent, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, di Ethers such as ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

Moreover, ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone, are mentioned as (E) organic solvent.

(E) As an organic solvent, aromatic hydrocarbons, such as toluene and xylene, are mentioned preferably, for example.

When these (E) organic solvents contain the solubility of each component contained in the photosensitive coloring composition, and an alkali-soluble binder, it is also preferable to mix 2 or more types from a viewpoint of the solubility, the improvement on a coating surface, etc. In this case, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, It is especially preferable that it is a mixed solution which consists of 2 or more types chosen from the group which consists of ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol monomethyl ether acetate.

(E) The amount in which the total solid concentration in a composition becomes 10 mass%-80 mass% is preferable, and, as for content in the coloring photosensitive composition of the organic solvent, the amount which becomes 15 mass%-60 mass% is more preferable.

As mentioned above, although the essential component which comprises the photosensitive coloring composition of this invention was demonstrated centeringly, the photosensitive coloring composition of this invention can contain other components, such as a photoinitiator, a sensitizer, and surfactant as needed.

Other components are described below.

Other ingredients

Photopolymerization initiator

It is preferable that the photosensitive coloring composition of this invention contains at least 1 type of photoinitiator. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of properties, start efficiency, absorption wavelength, availability and cost.

As the photopolymerization initiator, for example, at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl substituted coumarin compound, a ropin dimer, a benzophenone compound, an acetophenone compound, and And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds. As a specific example of a photoinitiator, the thing of Paragraph [0070]-[0077] of Unexamined-Japanese-Patent No. 2004-295116 is mentioned. Especially, an oxime type compound is preferable from a point with which a polymerization reaction is rapid.

There is no restriction | limiting in particular as said oxime type compound (henceforth an "oxime type photoinitiator"), For example, it is described in Unexamined-Japanese-Patent No. 2000-80068, WO 02/100903 A1, Unexamined-Japanese-Patent No. 2001-233842, etc. An oxime type compound is mentioned.

Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4- (Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1,2-butanedione, 2 -(O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methyl Benzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane On, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone and 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) -9H -Carbazol-3-yl] ethanone and the like. However, it is not limited to these.

Moreover, in this invention, the compound represented by following General formula (1) is more preferable as an oxime type compound from a viewpoint of a sensitivity, time-lapse stability, and coloring at the time of post-heating.

In the general formula (1), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5.

As R, an acyl group is preferable from the point of high sensitivity, and an acetyl group, a propionyl group, a benzoyl group, or a toluyl group is specifically, preferable.

As A, the sensitivity is increased and the alkylene group substituted with an unsubstituted alkylene group and alkyl group (for example, methyl group, ethyl group, tert-butyl group, and dodecyl group) from the point which suppresses coloring by the time-lapse of a heating (example) For example, an alkylene group and an aryl group (e.g., phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) substituted with vinyl group, allyl group) The alkylene group substituted with is preferable.

As Ar, a substituted or unsubstituted phenyl group is preferable at the point which raises a sensitivity and suppresses coloring by time-lapse | heating. In the case of a substituted phenyl group, as the substituent, halogen groups, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, are preferable, for example.

As X, the alkyl group which may have a substituent, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, and the substituent may have from the point of solvent solubility and the absorption efficiency improvement of a long wavelength region. The alkoxy group, the aryloxy group which may have a substituent, the alkylthioxy group which may have a substituent, the arylthioxy group which may have a substituent, or the amino group which may have a substituent is preferable.

In addition, n in General formula (1) has a preferable integer of 1-2.

Moreover, you may use other well-known photoinitiator of Paragraph of Unexamined-Japanese-Patent No. 2004-295116 in addition to the said photoinitiator for the photosensitive coloring composition of this invention.

The photopolymerization initiator may be contained singly or in combination of two or more.

As for content (in the case of 2 or more types, total content) in the total solid of the photosensitive coloring composition of a photoinitiator, 3 mass%-20 mass% are preferable from a viewpoint of obtaining the effect of this invention more effectively, 4 mass%-19 mass % Is more preferable, and 5 mass%-18 mass% are especially preferable.

Increase / decrease agent

It is preferable to add a sensitizer further to the photosensitive coloring composition of this invention from a viewpoint of a sensitivity improvement. By exposing the wavelength which this sensitizer can absorb, the radical generating reaction of a photoinitiator component and the polymerization reaction of an ethylenically unsaturated compound by it are accelerated | stimulated.

As such a sensitizer, a well-known spectroscopic sensitizer or dye and dye or pigment which absorb light and interact with a photoinitiator are mentioned.

Preferred sensitizers that can be used in the present invention include the spectroscopic sensitizing dyes and dyes exemplified below.

Specifically, the cationic dye described in Unexamined-Japanese-Patent No. 62-143044; A quinoxalinium salt described in Japanese Patent Publication No. 59-24147; Shin methylene blue compound of Unexamined-Japanese-Patent No. 64-33104; Anthraquinones described in JP-A-64-56767; Benzoxanthan dyes described in JP-A-2-1714; The acridines described in JP-A-2-226148 and JP-A-2-226149; Pyrylium salts described in JP-A-40-28499; Cyanines described in Japanese Patent Publication No. 46-42363; A benzofuran colorant described in JP-A-2-63053; Conjugated ketone dyes disclosed in JP-A-2-85858 and JP-A-2-216154; The dye described in JP-A-57-10605; Azocinnamylidene derivatives described in Japanese Patent Application Laid-Open No. 2-30321; A cyanine dye described in JP-A-1-287105; A xanthan-based dye described in JP-A-62-31844, JP-A-62-31848 and JP-A-62-143043; Aminostyryl ketones disclosed in Japanese Patent Publication No. 59-28325; The dye described in JP-A-2-179643; Merocyanine coloring matter disclosed in JP-A-2-244050; Merocyanine coloring matter disclosed in Japanese Patent Publication No. 59-28326; A merocyanine coloring matter described in JP-A-59-89303; Merocyanine coloring matter disclosed in JP-A-8-129257; And benzopyran pigments described in JP-A-8-334897.

As another preferable embodiment of a sensitizer, the pigment | dye which belongs to the following compound groups and has a maximum absorption wavelength in 350-450 nm is mentioned.

Specific examples thereof include polynuclear aromatics (for example, pyrene, perylene, and triphenylene), xanthenes (for example, fluorescein, eosin, erythrosin, rhodamine B, and rose bengal), and cyanines (for example, For example, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), Acridines (for example, acridine orange, chloroflavin, acriflavin), anthraquinones (for example anthraquinone) and squarylium (for example, squarylium) are mentioned. .

It is preferable that content of a sensitizer is 0.01 mass% or more and less than 5 mass% with respect to the total solid of the photosensitive coloring composition on a mass basis, More preferably, it is 0.1 mass% or more and less than 5 mass%, Especially preferably, it is 0.3 mass% or more 2 It is mass% or less. If content of a sensitizer is in this range, there will be no coloring, it is highly sensitive, and the photosensitive coloring composition with a good pattern formation property can be obtained.

Alkali soluble binder

The alkali-soluble binder is not particularly limited except for a binder having alkali solubility. Preferably, the alkali-soluble binder can be selected from the viewpoints of heat resistance, developability and availability.

The alkali-soluble binder is preferably a linear organic high polymer, soluble in an organic solvent, and capable of being developed with a weak alkaline aqueous solution. Examples of such linear organic polymers include polymers having a carboxylic acid in the side chain, such as Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication 54 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid described in each of Japanese Patent Application Laid-Open No. 25957, Japanese Patent Publication No. 59-53836, and Japanese Patent Publication No. 59-71048 Copolymers and partially esterified maleic acid copolymers; and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

As the alkali-soluble binder in the present invention, in addition to the above, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylates), such as those obtained by adding an acid anhydride to a polymer having a hydroxyl group, Polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful. In addition, the linear organic polymer may be a polymer obtained by copolymerizing a monomer having hydrophilicity. Examples of such polymers include alkoxyalkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, glycerol (meth) acrylates, (meth) acrylamides, N-methylol acrylamides, secondary or tertiary alkylacrylamides. , 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, etc. are mentioned. Other monomers having hydrophilicity include tetrahydrofurfuryl group, phosphoric acid group, phosphate ester group, quaternary ammonium base group, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group or group derived from salts thereof, or morpholinoethyl group. The monomer etc. which are formed are also useful.

In addition, the alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency. For example, the polymer etc. which contain an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in a side chain are also useful. As an alkali-soluble binder which has a polymeric group, alkali-soluble resin etc. which contain an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in a side chain are useful. Examples of the alkali-soluble binder containing the polymerizable group include Dial NR series (manufactured by MITSUBISHI RAYON CO., LTD.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscot R- 264 and KS Resist 106 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), Cyclomer P Series and Plaxel CF200 Series (both manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) And Ebecryl3800 (made by DAICEL-UCB Company LTD.). have.

In addition, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful in order to increase the strength of the cured coating film.

Among these various alkali-soluble binders, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins and acrylic / acrylamide copolymer resins are preferable from the viewpoint of heat resistance, and acrylic resins from the viewpoint of developability control. , Acrylamide resins and acryl / acrylamide copolymer resins are preferred.

As said acrylic resin, the copolymer consisting of a monomer chosen from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, etc., KS resist-106 of a commercial item (OSAKA ORGANIC CHEMICAL) INDUSTRY LTD.) And Cyclomer P series (DAICEL CHEMICAL INDUSTRIES, LTD.) Etc. are preferable.

As the alkali-soluble binder, the developability and liquid weight average molecular weight of the polymer 1000~2 10 × (a polystyrene conversion value measured by GPC method) ⁵ from the viewpoint of viscosity are preferred, than the 2000~1 10 × ⁵ polymer It is preferable and the polymer which is 5000-5 * 10 <^4> is especially preferable.

Cross-linking agent

By using a crosslinking agent complementarily to the photosensitive coloring composition of this invention, the hardness of the colored cured film formed by hardening | curing the photosensitive coloring composition can also be made higher.

The crosslinking agent is not particularly limited as long as it can perform film curing by a crosslinking reaction. Examples of the crosslinking agent include at least one substituent selected from the group consisting of (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group and an acyloxymethyl group. Substituted melamine compound, guanamine compound, glycoluril compound or urea compound and (c) phenolic compound, naphthol compound or hydroxyanthracene substituted with at least one substituent selected from the group consisting of methylol group, alkoxymethyl group and acyloxymethyl group The compound can be mentioned. Especially, polyfunctional epoxy resin is preferable.

For details, such as the specific example of a crosslinking agent, the description of Paragraph [0134]-[0147] of Unexamined-Japanese-Patent No. 2004-295116 can be referred.

Other additives

In addition, the photosensitive coloring composition of the present invention may contain various additives, for example, fillers, polymer compounds other than those described above, nonionic, cationic or anionic surfactants, adhesion promoters, antioxidants, ultraviolet absorbers and anti-aggregation agents as necessary. Etc. can be mix | blended. As an example of these additives, the thing of Paragraph [0155]-[0156] of Unexamined-Japanese-Patent No. 2004-295116 is mentioned.

The photosensitive coloring composition of this invention may contain the sensitizer and light stabilizer of Paragraph [0078] of Unexamined-Japanese-Patent No. 2004-295116, and / or the thermal polymerization inhibitor of Paragraph [0081] of the same publication.

Moreover, when promoting alkali solubility of a non-exposure area | region, and aiming at the further improvement of the developability of the photosensitive coloring composition, organic carboxylic acid, Preferably the low molecular weight organic carboxylic acid of molecular weight 1000 or less is added to the said composition. It is preferable.

Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capronic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid and Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid, and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melotropic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamonic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, coumalic acid and umbelic acid.

Preparation method of the photosensitive coloring composition

The coloring composition of this invention is prepared by mixing each component mentioned above and arbitrary components as needed.

In addition, in preparation of the photosensitive coloring composition, you may mix | blend each component which comprises a coloring composition collectively, and you may mix | blend sequentially after melt | dissolving and disperse | distributing each component to a solvent. In addition, the addition order and working conditions at the time of compounding are not restrict | limited. For example, a composition may be prepared by dissolving and dispersing all the components in a solvent at the same time. If necessary, each component may be suitably set as two or more solutions and dispersions. You may prepare.

However, when using a pigment as a component, it is preferable to prepare a coloring composition after disperse | distributing a pigment previously and making it as a pigment dispersion liquid.

The photosensitive coloring composition prepared as mentioned above, Preferably it can provide for use, after filtering-separating using a filter etc. about 0.01 micrometer-3.0 micrometers of hole diameters, More preferably, about 0.05 micrometers-0.5 micrometers of pore diameters. .

Since the photosensitive coloring composition of this invention is high brightness and can form the colored cured film excellent in color and contrast, such as a color filter used for a liquid crystal display device (LCD) or a solid-state image sensor (for example, CCD, CMOS, etc.) As a composition for colored pixel formation, it can be used suitably also for production uses, such as a printing ink, an inkjet ink, and a coating material.

Color filter and its manufacturing method

The color filter of this invention is provided by providing the board | substrate and the coloring pixel formed using the photosensitive coloring composition containing (D) dye on the said board | substrate. The colored area | region on a board | substrate comprises each pixel of a color filter, and is comprised by the colored film, such as red (R), green (G), and blue (B), for example. Since the color filter of this invention is formed including specific (D) dye, an image becomes high brightness and is excellent in color and contrast, especially as a color filter for a liquid crystal display device, an organic EL display device, or a solid-state image sensor. desirable.

The color filter of this invention may be formed by any method as long as it is a method of forming the colored area | region (coloring pattern) obtained by hardening | curing the photosensitive coloring composition of this invention.

The manufacturing method of the color filter of this invention provides the process (1) which gives the photosensitive coloring composition mentioned above on a support body, and forms a colored layer (it is also called a coloring composition layer), and the coloring composition layer formed in process (1) (preferably Preferably, it includes an exposure step (2) of exposing the latent image by forming a latent image by exposing the pattern image through a mask, and the step (3) of developing the colored layer on which the latent image is formed to form a colored region (colored pattern).

Moreover, especially the manufacturing method of the color filter of this invention irradiates an ultraviolet-ray with respect to the coloring pattern formed in the process (3), and the ultraviolet-ray is irradiated with respect to the coloring pattern formed in the process (3) or in the process (4). Embodiment which further includes the process (5) which heat-processes with respect to the irradiated coloring pattern is preferable.

Moreover, a color filter can also be manufactured by methods, such as the transfer method of Unexamined-Japanese-Patent No. 2009-116078, the inkjet method of Unexamined-Japanese-Patent No. 2009-134263, etc.

Hereinafter, the manufacturing method of the color filter of this invention is demonstrated more concretely.

Process (1)

In the manufacturing method of the color filter of this invention, the photosensitive coloring composition of this invention mentioned above is first apply | coated by the apply | coating methods, such as rotation coating, cast | flow_spreading, or roll coating, on a support body, and a coloring composition layer is formed after that as needed. Precuring (prebaking) is performed and the said coloring composition layer is dried.

Examples of the support include soda glass, alkali free glass, borosilicate glass, quartz glass, resin substrates, and the like used in liquid crystal displays and the like; CCD and CMOS for use in solid state imaging devices; A photoelectric conversion element substrate in an organic CMOS; And silicon substrates.

Moreover, you may form a primer layer on these support bodies in order to improve adhesion with an upper layer, to prevent the spread of a substance, or to planarize a surface as needed.

The coating composition of a coloring composition can be formed by apply | coating the coloring composition of this invention to a board | substrate directly or via another layer by rotation methods, slit application, cast | coating, roll application, bar application | coating, inkjet, etc.

As conditions for prebaking, the conditions of heating for about 0.5 to 15 minutes at 70 degreeC-130 degreeC using a hotplate and oven are mentioned.

In addition, the thickness of the coloring composition layer formed with a coloring composition is suitably selected according to the objective. In the color filter for liquid crystal display devices, the thickness of the coloring composition layer is preferably in the range of 0.2 µm to 5.0 µm, more preferably in the range of 1.0 µm to 4.0 µm, and most preferably in the range of 1.5 µm to 3.5 µm. Moreover, in the color filter for solid-state image sensors, the thickness of a coloring composition layer has the preferable range of 0.2 micrometer-5.0 micrometers, The range of 0.3 micrometer-2.5 micrometers is more preferable, The range of 0.3 micrometer-1.5 micrometers is the most preferable. .

In addition, the thickness of a coloring composition layer is the film thickness after prebaking.

Process (2)

Next, in the manufacturing method of the color filter of this invention, exposure is performed through the photomask, for example with respect to the coloring composition layer formed on the support body. As light or radiation which can be applied to exposure, g line | wire, h line | wire, i line | wire, KrF light, and ArF light are preferable, and i line | wire is especially preferable. When using i line | wire as irradiation light, it is preferable to irradiate with the exposure amount of 100mJ / cm <2> -10000mJ / cm <2>.

In addition, as other exposure light rays, ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light source fluorescent lamps, tungsten lamps, and sunlight can also be used. .

Exposure process using a laser light source

In an exposure method using a laser light source, an ultraviolet laser is used as a light source.

The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, and more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm matches the photosensitive wavelength of the resist. It is preferable at the point. Specifically, the third harmonic (355 nm) of the Nd: YAG laser of the solid laser having a large output and relatively low cost, and the XeCl (308 nm) and XeF (353 nm) of the excimer laser can be preferably used.

The exposure amount of a to-be-exposed object (pattern) is the range of 1mJ / cm <2> -100mJ / cm <2>, and the range of 1mJ / cm <2> -50mJ / cm <2> is more preferable. It is preferable at the point of productivity of pattern formation that an exposure amount is this range.

Although there is no restriction | limiting in particular as an exposure apparatus, As what is marketed, Callisto (made by V-Technology Co., Ltd.), EGIS (made by V-Technology Co., Ltd.), and DF2200G (made by DAINIPPON SCREEN MFG. CO., LTD.) ) Can be used. Apparatuses other than those described above are also preferably used.

You may heat the coloring composition layer exposed as mentioned above.

Further, the exposure can be performed while flowing nitrogen gas in the chamber in order to suppress oxidation and discoloration of the coloring material in the colored composition layer.

Process (3)

Subsequently, image development is performed using a developing solution with respect to the coloring composition layer after exposure. Thus, a colored pattern (resist pattern) can be formed.

As long as the developing solution melt | dissolves the unhardened part (unexposed part) of a coloring composition layer, and does not melt a hardened part (exposed part), the combination of various organic solvents or an alkaline aqueous solution can be used. When the developing solution is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 11-13, more preferably pH 11.5-12.5. As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen chloride, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide Alkaline aqueous solutions, such as a roxide, a choline, a pyrrole, a piperidine, and 1,8- diazabicyclo- [5,4,0] -7-undecene, are mentioned.

As for image development time, 30 second-300 second are preferable, More preferably, they are 30 second-120 second. As for image development temperature, 20 degreeC-40 degreeC are preferable, More preferably, it is 23 degreeC.

The development can be carried out by a puddle method, a shower method or a spray method.

Moreover, after developing using alkaline aqueous solution, it is preferable to wash with water.

Then, in the manufacturing method of the color filter of this invention, you may perform post-heating and / or post-exposure with respect to the coloring pattern formed by image development as needed, and accelerate hardening of a coloring pattern.

Process (4)

In the manufacturing method of the color filter of this invention, you may perform postexposure by ultraviolet irradiation with respect to the coloring pattern (pixel) formed using the coloring composition.

Process (5)

It is preferable to heat-process further about the coloring pattern in which postexposure by the above-mentioned ultraviolet irradiation was performed. The colored pattern can be further cured by heat treatment (so-called post-baking treatment) of the formed colored pattern. This heat treatment can be performed by, for example, a hot plate, various heaters or an oven.

It is preferable that the temperature at the time of heat processing is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. Moreover, as for heating time, about 10 to 120 minutes are preferable.

The coloring pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having pixels of a plurality of colors, the steps (1), (2), (3) and, if necessary, the step (4) and / or step (5) in accordance with the desired number of colors. You can repeat.

Moreover, every time formation, exposure, and image development of a monochromatic coloring composition layer are complete | performed (per every color), you may perform the said process (4) and / or the process (5), and all the coloring composition layers of a desired color number The step (4) and / or step (5) may be performed collectively after the formation, exposure, and development are completed.

The color filter (color filter of this invention) obtained by the manufacturing method of the color filter of this invention is high brightness in the point which uses the photosensitive coloring composition of this invention, and is excellent in color and contrast.

The color filter of the present invention can be used for a liquid crystal display element or a solid-state image pickup element, and is particularly suitable for use in liquid crystal display devices. When used for a liquid crystal display device, since dye is used as a colorant, display of an image excellent in spectral characteristics and contrast can be achieved while achieving good color.

Liquid Crystal Display, Organic EL Display

The liquid crystal display device and organic electroluminescence display of this invention are equipped with the color filter of this invention mentioned above.

About the definition of a liquid crystal display device and an organic electroluminescent display, and the detail of each display device, for example, "Electronic display device (Aki Sasaki-Kyo, Industrial Co., Ltd., 1990 issuance)" and "Display device (Ibuki Sumakiiser) , 1989 Industrial Co., Ltd.). In addition, about a liquid crystal display device, it describes in the "next-generation liquid crystal display technology (Tatsuo Uchida editorial, 1994). There is no restriction | limiting in particular in the system of the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in the said "next-generation liquid crystal display technology."

The color filter of this invention is especially effective especially with respect to the liquid crystal display device of a color TFT system. About the liquid crystal display device of a color TFT system, it describes in the "color TFT liquid crystal display (public publication Co., Ltd. 1996 issuance), for example." Further, the present invention can also be applied to liquid crystal display devices having enlarged viewing angles such as transverse electric field driving methods such as IPS and pixel division methods such as MVA, STN, TN, VA, OCS, FFS, and R-OCB.

In addition, the color filter of the present invention can be provided in a bright and high-precision color filter on array (COA) method.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a three-wavelength tube of a conventionally known cold cathode tube, and the luminance is high by using a red, green, and blue LED light source (RGB-LED) as a backlight. In addition, a liquid crystal display device having good color reproducibility having high color purity can be provided.

Moreover, the color filter of this invention can be used for solid-state image sensors, such as CCD and CMOS, and when used for a solid-state image sensor, it is possible to provide a color filter with high brightness and good color resolving ability.

Example

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples without departing from the spirit thereof. In addition, "part" and "%" are mass references | standards unless there is particular notice.

First, each structural component used for the Example and the comparative example is demonstrated.

(A-6): (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone)

(A-7): 2- (benzoyloxyimino) -1- [4 '-(phenylthio) phenyl] -1-octanone (manufactured by Ciba Specialty Chemicals; IRGACURE OXE 01)

(B-1): ethylene glycol bis (3-mercaptobutyrate)

(B-2): 1,2-propylene glycol bis (3-mercapto butyrate)

(B-3): trimethylolpropane tris (3-mercaptobutyrate)

(B-4): ethylene glycol bis (2-mercapto isobutyrate)

(B-5): 1,2-propylene glycol bis (2-mercapto isobutyrate)

(B-6): trimethylolpropane tris (2-mercaptoisobutyrate)

(B-7): pentaerythritol tetrakis (3-mercaptobutyrate)

(B-8): 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione

(B-9): pentaerythritol tetrakis (3-mercaptopropionate)

(B-10): N-phenyl2-mercaptobenzoimidazole

(C-1): Nippon Kayaku Co., Ltd., KAYARAD DPHA

(C-2): Toagosei Co., Ltd. Article, aronix TO-2349

(D-1): Dye compound represented by following structural formula (7)

(D-2): Dye compound represented by following structural formula (9)

(D-3): Dye compound represented by the following structural formula

(D-4): dye compound represented by the following structural formula

(D-5): Dye compound represented by the following structural formula

(D-6): dye compound represented by the following structural formula

(D-7): Pigment yellow liquid obtained by mixing Pigment Yellow 138 with 12 parts and 11 parts of acrylic pigment dispersants with 77 parts of propylene glycol monomethyl ether acetate, and fully disperse | distributing a pigment using a bead mill.

(D-8): dye compound represented by the following structural formula (20)

In addition, the solubility and absorption peak wavelength in 25 degreeC with respect to the propylene glycol monomethyl ether acetate of (D-1)-(D-6) and (D-8) which are dye compounds are shown in Table 1.

(E-1): pigment dispersion obtained by mixing C.I. pigment green 58 with 15 parts and 8.4 parts of acrylic pigment dispersants with 76.6 parts of propylene glycol monomethyl ether acetate and sufficiently dispersing the pigment using a bead mill.

(F-1): alkali-soluble binder: allyl methacrylate / methacrylic acid (solid content 20.0%)

(G-1): solvent: propylene glycol monomethyl ether acetate

(G-2): Solvent: ethyl 3-ethoxypropionate

(H-1): Surfactant: Megapack F475 (manufactured by DIC Corporation)

Example 1

Preparation of the photosensitive coloring composition

Each component described in the following composition was mixed and the photosensitive coloring composition was prepared.

<Composition>

(A-1) above 0.5 parts

(B-1) above 1.0 parts

(C-1) above 4.5 parts

(D-1), above 3.0 parts

(E-1) above ... 28.0 parts

(F-1) above 10.0 parts

(G-1) above ... 28.3parts

(G-2) above ... 24.6 parts

(H-1), above 0.06 parts

Examples 2-16, Comparative Examples 1-7

Each component of (A-1), (B-1), and (D-1) in Example 1 is changed to each component of Table 1, and except for the same as Example 1, Examples 2-16. And the photosensitive coloring composition of Comparative Examples 1-7 was prepared. In addition, in the Example and the comparative example which changed (D-1) to (D-2)-(D-8) for the comparison of brightness, the quantity of (E-1) was changed, and the C light source of a coating film The chromaticity of was adjusted so that x = 0.29 and y = 0.59.

evaluation

About each photosensitive coloring composition obtained above, sensitivity, brightness | luminance, and storage stability were evaluated by the following method.

Sensitivity

About the photosensitive coloring composition prepared in each Example and the comparative example, it irradiated to the coating film using the i line | wire reduction projection exposure apparatus so that the exposure amount might be 50mJ / cm <2> through a mask of 20 micrometers x 20 micrometers in length of 365 nm. . After the irradiation, the coating film was developed at 23 ° C. for 60 seconds using a developing solution (trade name: CD-2000, 60%, manufactured by FUJIFILM Electronic Materials CO., LTd.). Subsequently, after rinsing with running water for 20 seconds, it was spray dried to obtain a pattern image. Image formation was confirmed by an optical microscope. The larger the width of the obtained pixel pattern is, the more sensitive it is. The width of the obtained pixel pattern was determined by the following criteria.

Criteria

A: 35 micrometers or more

B: 30 micrometers or more and less than 35 micrometers

C: 20 micrometers or more and less than 30 micrometers

D: less than 20 μm

Luminance

About the photosensitive coloring composition prepared in each Example and the comparative example, after apply | coating the photosensitive coloring composition obtained above on the glass (# 1737; Corning Incorporated) by a spin coat method, it volatilized for 3 minutes at 100 degreeC, and coloring it. A composition film was formed. After cooling, the coloring composition film was exposed using an ultrahigh pressure mercury lamp. The irradiation light amount was 100 mJ / cm 2. Subsequently, postbaking was performed at 230 degreeC for 20 minutes, and the glass substrate which has a colored layer with a film thickness of 2 micrometers was obtained. The chromaticity of the glass substrate which has a colored layer was measured using the optical microscope spectrometer OSP-SP200 made from Olympus Corporation, and Y value at the time of chromaticity of x = 0.29 and y = 0.59 was measured with C light source. The higher the Y value, the better the color performance for the liquid crystal display device. The Y value was determined by the following criteria.

Criteria

A: Y value 57 or more

B: Y value 56 or more and less than 57

C: Y value 55 or more and less than 56

D: Y value less than 55

Storage stability

The photosensitive coloring composition prepared in each Example and the comparative example was put into the glass preservation bottle, it heated at 40 degreeC for 72 hours in the dryer, and measured the viscosity of the photosensitive coloring composition before and behind heating. The numerical value of viscosity after heating / viscosity before heating was computed, and it judged by the following criteria. The closer this number is to 1, the better the storage stability.

In addition, E type viscometer (made by TOKI SANGYO CO., LTD.) Was used for the measurement of a viscosity, and measurement temperature was 25 degreeC.

Criteria

A: 0.95 or more but less than 1.05

B: 1.05 or more and less than 1.20

C: 1.20 or more but less than 1.40

D: 1.40 or more

The evaluation results are shown in Table 2. It is not practical for any one to have a D decision.

In Table 2, "A" at the top of the second row represents the initiator component represented by A-1 to A-7, and "B" at the top of the third row is a thiol compound represented by B-1 to B-10. "D" at the top of the fourth row represents the dye represented by D-1 to D-9.

From Table 2, in the Example of this invention, it was excellent in sensitivity and brightness | luminance, and storage stability was also favorable. On the other hand, in the comparative examples 2 and 7 which did not use the secondary polyfunctional thiol compound, the sensitivity or storage stability was bad, and the comparative examples 1 and 4 which did not use the hexaaryl bisimidazole represented by General formula (I). , 5 was low in sensitivity and / or brightness.

Claims (13)

(A) 1 mass at 25 ° C in hexaarylbisimidazole represented by the following general formula (I), (B) secondary polyfunctional thiol compound, (C) polymerizable compound, and (D) propylene glycol monomethyl ether acetate A dye having a solubility of not less than% and having an absorption peak wavelength of 420 to 480 nm and an organic solvent (E), wherein the content of the dye (D) is 5% by mass or more based on the total solids of the photosensitive coloring composition. Photosensitive coloring composition for color filters.

[Formula (I) of R ¹ ~R ³⁰ represents a chlorine atom, a hydrogen atom or an alkoxy group independently. The number of hydrogen atoms in R ¹ to R ³⁰ is 22 to 29, the number of substitution of chlorine atoms is 0 to 4 and the number of substitution of alkoxy groups is 1 to 4; The method of claim 1,
Said (B) secondary polyfunctional thiol compound is bivalent, The photosensitive coloring composition for color filters characterized by the above-mentioned. The method of claim 1,
The secondary polyfunctional thiol compound (B) includes ethylene glycol bis (3-mercaptobutyrate), 1,2-propylene glycol bis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), and It is at least 1 sort (s) chosen from the group which consists of 1, 2- propylene glycol bis (2-mercapto isobutyrate), The photosensitive coloring composition for color filters characterized by the above-mentioned. The method of claim 1,
(F) C. I. Pigment Green 58 It further contains the photosensitive coloring composition for color filters. The method of claim 1,
The said (D) dye is at least 1 sort (s) chosen from the group which consists of dye represented by the following general formula (II), general formula (III), and general formula (IV), The photosensitive coloring composition for color filters.

[In Formula (II), R ⁵¹ is an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, and an alkoxy having 2 to 12 carbon atoms. substituted with a group having a carbon number of 2 to 12 alkyl group, L ⁷¹ -CO-OL ⁷² - indicated that the alkyl carboxylic ^{group, L 73 -O-CO-L} 74 in - alkyloxycarbonyl group represented by, 1 to 20 carbon atoms The phenyl group substituted by the alkyl group or C1-C20 alkyl group substituted by the phenyl group is shown. L ⁷¹ represents an alkyl group having 2 to 12 carbon atoms, L ⁷² represents an alkylene group having 2 to 12 carbon atoms, L ⁷³ represents an alkyl group having 2 to 12 carbon atoms, and L ⁷⁴ represents an alkylene group having 2 to 12 carbon atoms. R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group or a halogen atom]

[In General Formula (III), (IV), R ⁶¹ to R ⁶⁵ and R ⁷¹ to R ⁷⁴ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, and an aryl group. Or heteroaryl group] The method of claim 1,
Content of the hexaarylbisimidazole represented by said (A) general formula (I) is 0.1%-10% by mass with respect to solid content of the photosensitive coloring composition, The photosensitive coloring composition for color filters characterized by the above-mentioned. The method of claim 1,
Content of the said (B) secondary polyfunctional thiol compound is 0.1%-10% by mass basis with respect to solid content of the photosensitive coloring composition, The photosensitive coloring composition for color filters characterized by the above-mentioned. The method of claim 1,
1 mass% or more of soluble in said (D) propylene glycol monomethyl ether acetate at 25 degreeC, and content of the dye whose absorption peak wavelength is 420-480 nm is 5%-30% by mass with respect to solid content of the photosensitive coloring composition. It is a photosensitive coloring composition for color filters. It has the colored layer formed using the photosensitive coloring composition for color filters in any one of Claims 1-8, The color filter characterized by the above-mentioned. The colored layer formation process of providing the photosensitive coloring composition for color filters of any one of Claims 1-8 on a support body, and forming a colored layer,
An exposure step of forming a latent image by exposing a pattern image to the colored layer;
And a developing step of developing a colored layer on which the latent image is formed to form a pattern. The color filter of Claim 9 was provided. The liquid crystal display device characterized by the above-mentioned. An organic EL display device comprising the color filter according to claim 9. The color filter of Claim 9 was provided, The solid-state image sensor characterized by the above-mentioned.