JP2007322744A - Colored photosensitive resin composition, photosensitive resin transfer material, color filter, its manufacturing method, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition which has fine chromaticity and is highly sensitive when hardened and suitable for color filters, and also to provide a photosensitive resin transfer material, a color filter and its manufacturing method, and a liquid crystal display thereof. <P>SOLUTION: The colored photosensitive resin composition contains a binder, a polymerized compound, a photopolymerizing initiator, and coloring agents. The photopolymerizing initiator is an oxime ester compound expressed in the general formula (1). In the general formula (1), R<SP>1</SP>represents an alkyl group or the like, and R<SP>2</SP>represents any one of an alkyl group, an alkyl oxy group, an aryl oxy group, an alkylthio group, an arylthio group, a halogen atom, and an alkyl oxy-carbonyl group, and further, Ar represents an aromatic ring, A represents a ring of 4 or 7 members, and m represents zero or a larger integer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a colored photosensitive resin composition and a photosensitive resin transfer material suitable for a color filter used in a liquid crystal display device (LCD) such as a notebook computer and a television monitor, and the colored photosensitive resin composition and the The present invention relates to a color filter made of a photosensitive resin transfer material, a manufacturing method thereof, and a liquid crystal display device using the color filter.

  The color filter is an indispensable component for a liquid crystal display (hereinafter sometimes referred to as “liquid crystal display device”). This liquid crystal display is very compact, is equivalent to or better than conventional CRT displays in terms of performance, and is replacing the CRT displays.

  In the formation of a color image of the liquid crystal display, the light passing through the color filter is colored as it is into the color of each pixel constituting the color filter, and the light of those colors is synthesized to form a color image. At present, a color image is formed with pixels of three colors of RGB.

Further, in the liquid crystal display device, the distance between the TFT substrate and the color filter, that is, the thickness of the liquid crystal layer (cell gap), in other words, the distance between two electrodes that apply an electric field to the liquid crystal in the display region is uniform. Greatly affects the quality of images.
Usually, in order to keep the cell gap constant, the thickness and height of the spacer, the black matrix, the colored layer (red, green, blue layer) and the like need to be uniform. Initially, inorganic particles such as silica were used as spacers.
However, this method has a problem that fine particles are present in the pixel and the image quality is deteriorated.

Therefore, in recent years, proposals have been made to form columnar formations (hereinafter sometimes referred to as “columnar spacers”) by photolithography using a photosensitive resin composition.
However, in a photosensitive resin composition for producing a color filter or a black matrix layer, a difference in crosslink density between an exposed part and an unexposed part is given due to the high light shielding ability of either a coloring pigment or a dye. However, since a large amount of exposure energy is required, productivity is not improved.

Moreover, in order to raise the sensitivity of the photosensitive resin composition, the thing containing the highly reactive photoinitiator is proposed (refer patent document 1 and 2).
However, even this photosensitive resin composition has a problem that it is difficult to form a fine pattern because of insufficient sensitivity.

  For this reason, a colored photosensitive resin composition having good color purity, high sensitivity upon curing, and capable of forming a high-definition pattern has not yet been provided, and further improvement and development are desired. The current situation is rare.

JP 2000-80068 A JP-T-2004-534797

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention has good chromaticity, high sensitivity at the time of curing, and can form a high-definition pattern, and is particularly used for liquid crystal display devices such as displays for notebook computers and TV monitors. Colored photosensitive resin composition suitable for color filter, photosensitive resin transfer material comprising the colored photosensitive resin composition, and color filter comprising the colored photosensitive resin composition or the photosensitive resin transfer material An object of the present invention is to provide a manufacturing method thereof and a liquid crystal display device using the color filter.

Means for solving the problems are as follows. That is,
<1> A colored photosensitive resin composition comprising a binder, a polymerizable compound, a photopolymerization initiator, and a colorant, wherein the photopolymerization initiator is represented by the following general formula (1). It is a colored photosensitive resin composition characterized by being a compound.
However, in said general formula (1), R < ¹ > represents either an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, and R < ² > is an alkyl group, an alkyloxy group, an aryloxy group, and an alkylthio group. , An arylthio group, a halogen atom, and an alkyloxycarbonyl group, Ar represents either an aromatic ring or a heteroaromatic ring, and A represents a 4-membered ring, 5-membered ring, or 6-membered ring , And any one of 7-membered rings, and m represents an integer of 0 or more. R ¹ and A may be further substituted with a substituent. When m represents an integer of 2 or more, the R ² may be the same as or different from each other.
<2> The colorant is pigment C.I. I. P. R. 254, and pigment C.I. I. P. R. 177. The colored photosensitive resin composition according to <1>, which is any one of 177.
<3> The colorant is pigment C.I. I. P. G. 36, pigment C.I. I. P. Y. 150, and pigment C.I. I. P. Y. 138. The colored photosensitive resin composition according to <1>, which is any one of 138.
<4> The colorant is pigment C.I. I. P. B. 15: 6, and pigment C.I. I. P. V. 23. The colored photosensitive resin composition according to <1>, which is any one of No. 23.
<5> Pigment C.I. I. P. R. 254, and pigment C.I. I. P. R. The colored photosensitive resin composition according to <2>, wherein the content of 177 is 5 to 60% by mass and 5 to 60% by mass with respect to the total solid content of the colored photosensitive resin composition, respectively. is there.
<6> Pigment C.I. I. P. G. 36, pigment C.I. I. P. Y. 150, and pigment C.I. I. P. Y. The coloring according to <3>, wherein the content of 138 is 5 to 60% by mass, 1 to 20% by mass, and 1 to 20% by mass with respect to the total solid content of the colored photosensitive resin composition, respectively. It is a photosensitive resin composition.
<7> Pigment C.I. I. P. B. 15: 6, and pigment C.I. I. P. V. The colored photosensitive resin composition according to <4>, wherein the content of 23 is 5 to 60% by mass and 0.1 to 10% by mass with respect to the total solid content of the colored photosensitive resin composition, respectively. It is a thing.
<8> The colored photosensitive resin composition according to <1>, wherein the colorant is a black pigment.
<9> The colored photosensitive resin composition according to any one of <1> to <8>, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).
In the general formula (2), R ¹ represents any of an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, and R ² represents an alkyl group, an alkyloxy group, an aryloxy group, and an alkylthio group. , An arylthio group, a halogen atom, and an alkyloxycarbonyl group, Ar represents an aromatic ring or a heteroaromatic ring, and A ¹ represents any of a 5-membered ring and a 6-membered ring. X ¹ represents either an oxygen atom or a sulfur atom, and m represents an integer of 0 or more. R ¹ and A ¹ may be further substituted with a substituent. When m represents an integer of 2 or more, the R ² may be the same as or different from each other.
<10> The colored photosensitive resin composition according to <9>, wherein the compound represented by the general formula (2) is a compound represented by any one of the following general formulas (3) and (4).
However, in said general formula (3) and (4), R < ⁶ > and R < ⁸ > represents either an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, and an alkyloxycarbonyl group. R ⁷ and R ⁹ represent either an alkyl group or an alkyloxy group, X ² and X ³ represent either an oxygen atom or a sulfur atom, and A ² and A ³ represent a 5-membered ring And 6 or a 6-membered ring, and p and q each represent an integer of 0 to 6.
<11> The colored photosensitive resin composition according to any one of <1> to <10>, including a surfactant.

<12> A photosensitive resin transfer material comprising a temporary support and a photosensitive resin layer, wherein the photosensitive resin layer is the colored photosensitive resin composition according to any one of <1> to <11>. It is the photosensitive resin transfer material characterized by comprising.
<13> The photosensitive resin layer according to <12>, wherein the photosensitive resin layer is obtained by applying and drying the colored photosensitive resin composition according to any one of <1> to <11> with a slit nozzle. It is a photosensitive resin transfer material.

<14> A color filter comprising a substrate and a photosensitive resin layer, wherein the photosensitive resin layer is the colored photosensitive resin composition according to any one of <1> to <11>, or the <12 > To <13>. A color filter formed using the photosensitive resin transfer material according to any one of <1> to <13>.
<15> The photosensitive resin layer according to <14>, wherein the photosensitive resin layer is attached to a substrate with a laminator using the photosensitive resin transfer material according to any one of <12> to <13>. It is a color filter.
<16> The photosensitive resin layer includes a red (R) photosensitive resin layer, a green (G) photosensitive resin layer, a blue (B) photosensitive resin layer, and a black matrix photosensitive resin layer, The red (R) photosensitive resin layer is composed of the colored photosensitive resin composition according to any one of <2>, <5>, <9>, <10>, and <11>, and the green (G ) The photosensitive resin layer is composed of the colored photosensitive resin composition according to any one of <3>, <6>, <9>, <10>, and <11>, and the blue (B) photosensitive property. The resin layer is composed of the colored photosensitive resin composition according to any one of <4>, <7>, <9>, <10>, and <11>, and the black matrix photosensitive resin layer is <8>, <9>, <10>, and the colored photosensitive resin composition according to any one of <11> The color filter according to <14>.

  <17> A photosensitive resin layer from the colored photosensitive resin composition according to any one of <1> to <11> or the photosensitive resin transfer material according to any one of <12> to <13>. A photosensitive resin layer forming step to be formed, an exposure step of exposing the photosensitive resin layer, a developing step of developing the photosensitive resin layer exposed by the exposing step, and a photosensitive resin developed by the developing step And a curing process for curing the layer.

  <19> A liquid crystal display device using the color filter according to any one of <14> to <16>.

  According to the present invention, it has good chromaticity, has high sensitivity at the time of curing, and can form a high-definition pattern, and is particularly used for liquid crystal display devices such as notebook computer displays and TV monitors. Colored photosensitive resin composition suitable for color filter, photosensitive resin transfer material comprising the colored photosensitive resin composition, and color filter comprising the colored photosensitive resin composition or the photosensitive resin transfer material , A manufacturing method thereof, and a liquid crystal display device using the color filter can be provided.

  First, the colored photosensitive resin composition of the present invention will be described, and then the photosensitive resin transfer material, color filter, manufacturing method thereof, and liquid crystal display device of the present invention will be sequentially described.

(Colored photosensitive resin composition)
The colored photosensitive resin composition of the present invention includes at least a binder, a polymerizable initiator, a photopolymerization initiator, and a colorant, and if necessary, a colored photosensitive resin including other components. The composition is characterized in that the photopolymerization initiator is a compound represented by the following general formula (1).
The colored photosensitive resin composition of the present invention includes the binder, the polymerizable compound, the photopolymerization initiator that is a compound represented by the following general formula (1), and the colorant. It has good chromaticity, has high sensitivity during curing, and can form a high-definition pattern.
However, in said general formula (1), R < ¹ > represents either an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, and R < ² > may mutually be same or different. Well, it represents any of an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, and an alkyloxycarbonyl group, and Ar represents either an aromatic ring or a heteroaromatic ring. , A represents any of a 4-membered ring, a 5-membered ring, a 6-membered ring, and a 7-membered ring, and m represents an integer of 0 or more. R ¹ and A may be further substituted with a substituent.

<Binder>
There is no restriction | limiting in particular as said binder, It can select suitably from well-known things, For example, an alkali-soluble binder is mentioned.
There is no restriction | limiting in particular as said alkali-soluble binder, Although it can select suitably from well-known things, For example, the polymer which has polar groups, such as a carboxylic acid group and a carboxylate group, is mentioned in a side chain.
Examples of the polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain include, for example, JP-A No. 59-44615, JP-B No. 54-34327, JP-B No. 58-12577, Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid as described in Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Application Laid-Open No. 59-53836 and Japanese Patent Application Laid-Open No. 59-71048 Examples thereof include a copolymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer.
Examples of the binder include a cellulose derivative having a carboxylic acid group in the side chain, and a polymer having a hydroxyl group to which a cyclic acid anhydride is added.
Examples of the binder include copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid, and other monomers. And multi-component copolymers are particularly preferred.
Examples of the binder include ordinary film-forming polymers in addition to polymers having these polar groups.
These binders may be used individually by 1 type, and may use 2 or more types together.
As solid content of the said binder, 20-50 mass% is preferable with respect to the total solid content of the colored photosensitive resin composition of this invention, for example, and 25-45 mass% is more preferable.

<Polymerizable compound>
The polymerizable compound is preferably, for example, any of a monomer and an oligomer that have two or more ethylenically unsaturated double bonds and undergo addition polymerization upon irradiation with light.
Examples of the monomer and oligomer include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure.
Specific examples of the monomer and oligomer include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) Acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol Tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Tri (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; Mention may be made of polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as methylolpropane and glycerin and then (meth) acrylated.
Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, described in Japanese Patent Publication No. 52-30490.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 is preferable.
The said polymeric compound may be used individually by 1 type, and may use 2 or more types together.
As solid content of the said polymeric compound, 5-50 mass% is preferable with respect to the total solid content of the colored photosensitive resin composition of this invention, for example, and 10-40 mass% is more preferable.

<Photopolymerization initiator>
The said photoinitiator is a compound represented by following General formula (1), The other photoinitiator can be used together as needed.

-Compound represented by the general formula (1)-
When the photopolymerization initiator includes a photopolymerization initiator represented by the following general formula (1), a color filter can be produced with a low exposure (high sensitivity), and the manufacturing time of the color filter is shortened. (Cost reduction).
However, in said general formula (1), R < ¹ > represents either an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, and R < ² > may mutually be same or different. Well, it represents any of an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, and an alkyloxycarbonyl group, and Ar represents either an aromatic ring or a heteroaromatic ring. , A represents any of a 4-membered ring, a 5-membered ring, a 6-membered ring, and a 7-membered ring, and m represents an integer of 0 or more. R ¹ and A may be further substituted with a substituent.

In the general formula (1), the acyl group in R ¹ is not particularly limited and may be appropriately selected from known ones, and examples thereof include aliphatic, aromatic, and heterocyclic rings.
The acyl group may be further substituted with a substituent. Examples of the substituent include an alkyloxy group, an aryloxy group, and a halogen atom.
As a total carbon number of the said acyl group, 2-30 are preferable, for example, 2-20 are more preferable, and 2-16 are especially preferable.
Specific examples of the acyl group are not particularly limited and may be appropriately selected from known ones. For example, acetyl group, propanoyl group, methylpropanoyl group, butanoyl group, pivaloyl group, hexanoyl group, cyclohexanecarbonyl Group, octanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, benzylcarbonyl group, phenoxyacetyl group, 2-ethylhexanoyl group, chloroacetyl group, benzoyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl group 1-naphthoyl group, 2-naphthoyl group, pyridylcarbonyl group, furanoyl group, thiophenoyl group, methacryloyl group, acryloyl group, and the like.

In the general formula (1), the total carbon number of the alkyloxycarbonyl group in R ¹ is preferably 2 to 30, more preferably 2 to 20, and particularly preferably 2 to 16.
The alkyloxycarbonyl group may be further substituted with a substituent.
Specific examples of the alkyloxycarbonyl group are not particularly limited and may be appropriately selected from known ones. For example, a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonylbutoxycarbonyl group, an isobutyloxycarbonyl group, Examples include allyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, ethoxyethoxycarbonyl group, and the like.

In the general formula (1), the total carbon number of the aryloxycarbonyl group in R ¹ is preferably 7 to 30, more preferably 7 to 20, and particularly preferably 7 to 16.
The aryloxycarbonyl group may be further substituted with a substituent.
Specific examples of the aryloxycarbonyl group are not particularly limited and may be appropriately selected from known ones. For example, phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5 -Diethoxyphenoxycarbonyl group, parachlorophenoxycarbonyl group, paranitrophenoxycarbonyl group, paracyanophenoxycarbonyl group, etc. are mentioned.

In the general formula (1), the alkyl group in R ² is not particularly limited and may be appropriately selected from known ones, such as a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, a tertiary group. A octyl group, and the like.
In the general formula (1), the alkyloxy group in R ² is not particularly limited and may be appropriately selected from known ones such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Can be mentioned.
In the general formula (1), the aryloxy group in R ² is not particularly limited and may be appropriately selected from known ones, such as benzyloxy group, phenoxy group, 4-chlorophenoxy group, 4 -Methylphenoxy group, and the like.
In the general formula (1), the alkylthio group in R ² is not particularly limited and may be appropriately selected from known ones. Examples thereof include a methylthio group, a butylthio group, an octylthio group, and a dodecylthio group. It is done.
In the general formula (1), the aryllthio group in R ² is not particularly limited and may be appropriately selected from known ones, such as a benzylthio group, a phenylthio group, a 4-methylphenylthio group, and the like. Is mentioned.
In the general formula (1), the halogen atom in R ² is not particularly limited and may be appropriately selected from known ones, and examples thereof include a chloro group, a bromo group, and an iodo group.
In the general formula (1), the alkyloxycarbonyl group in R ² is not particularly limited and may be appropriately selected from known ones, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.

In the general formula (1), the aromatic ring in Ar is not particularly limited and may be appropriately selected from known ones, and examples thereof include a benzene ring, a naphthalene ring, and an anthracene ring.
In the general formula (1), the heteroaromatic ring in Ar is not particularly limited and may be appropriately selected from known ones, such as pyrrole ring, indole ring, benzofuran ring, benzothiophene ring, etc. Is mentioned.

In the general formula (1), the 4-membered ring, 5-membered ring, 6-membered ring, and 7-membered ring in A are preferably formed by a ring-forming substituent. A may be a heterocycle.
Examples of the ring-forming substituent include alkylene, alkenylene, and alkynylene. The said ring-forming substituent may be used individually by 1 type, may use 2 or more types together, and may have an oxygen atom and a sulfur atom.
In the general formula (1), the 4-membered ring, 5-membered ring, 6-membered ring, and 7-membered ring in A may be further substituted with a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkyloxy group, an aryloxy group, and a halogen atom.

  In the general formula (1), m represents an integer of 0 or more, and can be appropriately selected depending on the structures of A and Ar.

The compound represented by the general formula (1) is preferably, for example, a compound represented by the following general formula (2). If the compound represented by the general formula (1) is a compound represented by the following general formula (2), the sensitivity can be improved.
In the general formula (2), R ¹ represents any of an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, and R ² represents an alkyl group, an alkyloxy group, an aryloxy group, and an alkylthio group. , An arylthio group, a halogen atom, and an alkyloxycarbonyl group, Ar represents an aromatic ring or a heteroaromatic ring, and A ¹ represents any of a 5-membered ring and a 6-membered ring. X ¹ represents either an oxygen atom or a sulfur atom, and m represents an integer of 0 or more. R ¹ and A ¹ may be further substituted with a substituent. When m represents an integer of 2 or more, the R ² may be the same as or different from each other.

Specific examples of the acyl group, alkyloxycarbonyl group, and aryloxycarbonyl group in R ¹ in the general formula (2) include, for example, the acyl group and alkyloxycarbonyl group in R ¹ in the general formula (1). And specific examples of the aryloxycarbonyl group.

In the general formula (2), specific examples of the alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, halogen atom, and alkyloxycarbonyl group in R ² include, for example, in the general formula (1) Specific examples of the alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, halogen atom, and alkyloxycarbonyl group in R ² are given.

  Specific examples of the aromatic ring and heteroaromatic ring in Ar in the general formula (2) include, for example, specific examples of the aromatic ring and heteroaromatic ring in Ar in the general formula (1). Can be mentioned.

In the general formula (2), the 5-membered ring and the 6-membered ring in A ¹ are preferably formed by a cyclic substituent. Specific examples of the cyclic substituent include specific examples of the cyclic substituent in A in the general formula (1).
In the general formula (2), the 5-membered ring and the 6-membered ring in A ¹ may be further substituted with a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkyloxy group, an aryloxy group, and a halogen atom.

As a compound represented by the said General formula (2), it is preferable that it is a compound represented by either the following general formula (3) and (4), for example. If the compound represented by the general formula (2) is a compound represented by any one of the following general formulas (3) and (4), the sensitivity can be further improved.
However, in said general formula (3) and (4), R < ⁶ > and R < ⁸ > represents either an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, and an alkyloxycarbonyl group. R ⁷ and R ⁹ represent either an alkyl group or an alkyloxy group, X ² and X ³ represent either an oxygen atom or a sulfur atom, and A ² and A ³ represent a 5-membered ring And 6 or a 6-membered ring, and p and q each represent an integer of 0 to 6.

In the general formulas (3) and (4), specific examples of the alkyl group in R ⁷ and R ⁹ are not particularly limited and may be appropriately selected from known ones, such as a methyl group and an ethyl group. Propyl group, butyl group, hexyl group, and the like. Among these, a methyl group, an ethyl group, and a propyl group are preferable in terms of high sensitivity.
In the general formulas (3) and (4), specific examples of the alkyloxy group in R ⁷ and R ⁹ are not particularly limited and may be appropriately selected from known ones, such as methoxy group, ethoxy Group, propoxy group, butoxy group, and the like.

Specific examples of the alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, halogen atom, and alkyloxycarbonyl group in R ⁶ and R ⁸ in the general formulas (3) and (4) include, for example, Specific examples of the alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, halogen atom, and alkyloxycarbonyl group in R ² in the general formula (1) can be given. Among these, an alkyloxy group, an arylthio group, and a halogen atom are preferable from the viewpoint of improving absorption efficiency.

Specific examples of the 5-membered ring and the 6-membered ring in A ² and A ³ in the general formulas (3) and (4) include, for example, the 5-membered ring in A in the general formula (1) and 6 Specific examples of member rings are given. Among these, a 5-membered ring is preferable in terms of sensitivity.

  In said general formula (3) and (4), p and q represent the integer in any one of 0-6, and it is preferable that it is 0-2.

Specific examples of the compounds represented by the general formulas (1), (2), (3), and (4) include the following formulas.

  The solid content of the compound represented by the general formula (1) is preferably 0.01 to 20% by mass with respect to the total solid content of the colored photosensitive resin composition of the present invention. More preferably, it is 1-10 mass%. If the solid content is less than 0.01% by mass, sufficient sensitivity may not be obtained, and if it exceeds 20% by mass, storage stability may be deteriorated.

-Other photopolymerization initiators-
As the photopolymerization initiator, other photopolymerization initiators other than the photopolymerization initiator represented by the general formula (1) can be used.
Examples of the other photopolymerization initiator include camphorquinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, α-hydroxycycloalkylphenyl ketone or 2-hydroxy-2-methyl-1-phenylpropanone, dialkyloxy Acetophenone, α-hydroxy- or α-amino-acetophenone, (4-methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 4-aroyl- 1,3-dioxolane, benzoin alkyl ethers and benzyl ketals (eg dimethylbenzyl ketal), phenylglyoxal esters and derivatives thereof, dimeric phenylglyoxal esters, diacesates And peresters (for example, benzophenone tetracarboxylic acid peresters described in European Patent No. 126,541), monoacylphosphine oxides (for example, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, bis Acylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6- Trimethylbenzoyl) -2,4-dipentoxyphenylphosphine oxide, trisacylphosphine oxide), halomethyltriazine (for example, 2- [2- (4-methoxyphenyl) vinyl] -4,6-bistrichloromethyl [1 , 3,5] triazine 2- (4-methoxyphenyl) -4,6-bistrichloromethyl [1,3,5] triazine, 2- (3,4-dimethoxyphenyl) -4,6-bistrichloromethyl [1,3,5] Triazine, 2-methyl-4,6-bistrichloromethyl [1,3,5] triazine, 2- (4-N, N-di (ethoxycarbonylmethylaminophenyl) -4,6-bis (trichloromethyl) [ 1,3,5] triazine, 2- (4-methoxynaphthyl) -4,6-bistrichloromethyl [1,3,5] triazine, 2- (1,3-benzodioxol-5-yl) -4,6 -Bistrichloromethyl [1,3,5] triazine, 2- [2- [4- (pentyloxy) phenyl] ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2 − ( 3-methyl-2-furanyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2- (5-methyl-2-furanyl) ethenyl] -4,6-bistrichloro Methyl [1,3,5] triazine, 2- [2- (2,4-dimethoxyphenyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2- (2- Methoxyphenyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2- (4-isopropyloxyphenyl) ethenyl] -4,6-bistrichloromethyl [1,3,5 ] Triazine, 2- [2- (3-Chloro-4-methoxyphenyl) ethenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2-Bromo-4-N, N- Di (ethoxy Rubonylmethyl) aminophenyl] -4,6-bistrichloromethyl [1,3,5] triazine, 2- [2-chloro-4-N, N-di (ethoxycarbonylmethyl) aminophenyl] -4,6- Bistrichloromethyl [1,3,5] triazine, 2- [3-Bromo-4-N, N-di (ethoxycarbonylmethyl) aminophenyl] -4,6-bistrichloromethyl [1,3,5] triazine 2- [3-chloro-4-N, N-di (ethoxycarbonylmethyl) aminophenyl] -4,6-bistrichloromethyl [1,3,5] triazine), other halomethyltriazines (for example, G . Buhr, R.A. Dammel and C.D. Lindley, Polym. Mater. Sci. Eng. 61,269 (1989), and compounds described in European Patent No. 022788), halomethyloxazole photoinitiators (eg, US Pat. Nos. 4,371,606 and 4,371,607). ), 1,2-disulfone hexaarylbisimidazole, and hexaarylbisimidazole (for example, compounds described in EA Bartmann, Synthesis 5,490 (1993)), coinitiators O-chlorohexaphenyl-bisimidazole in combination with systems (eg 2-mercaptobenzthiazole, ferrocenium compounds), titanocene (eg bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyrylphenyl) titanium) And a mixture thereof.

  As solid content of the said photoinitiator (the compound represented by the said General formula (1), and another photoinitiator), in the said coloring photosensitive resin composition total solid, 0.01- 20 mass% is preferable, 0.1-10 mass% is more preferable, 0.5-5 mass% is especially preferable.

<Sensitizer>
The sensitizer can improve sensitivity when producing a resin composition sensitive to light having a wavelength of 300 nm to 600 nm.
Specific examples of the sensitizer are not particularly limited and may be appropriately selected from known ones. For example, the sensitizers are described in paragraphs “0095” to “0099” of the specification of JP-T-2002-519732. Photosensitizers.
The content of the sensitizer is preferably 0.01 to 10% by mass with respect to the total solid content of the colored photosensitive resin composition.

<Colorant>
As the colorant, R (red) colored photosensitive resin composition (i), C.I. I. Pigment Red (C.I.P.R.) 254, and C.I. I. In the G (green) colored photosensitive resin composition (ii), any one of CI Pigment Red (C.I.P.R.) 177 is used. I. Pigment green (C.I.P.G.) 36, C.I. I. Pigment yellow (C.I.P.Y.) 150, and C.I. I. Any of CI Pigment Yellow (C.I.P.Y.) 138 is used, and in B (blue) colored photosensitive resin composition (iii), C.I. I. Pigment Blue (C.I.P.B.) 15: 6, and C.I. I. It is preferable to use any one of CI Pigment Violet (CIPV) 23 and a black pigment in the black matrix colored photosensitive resin composition (iv).

C. above. I. P. R. The content of 254 is preferably 5 to 60% by mass, and preferably 15 to 40% by mass with respect to the total solid content of the colored photosensitive resin composition (i). C. above. I. P. R. If the content of 254 is less than 5% by mass, the color may be light, and if it exceeds 60% by mass, it may be difficult to adjust various performances such as developability.
C. above. I. P. R. The content of 177 is preferably 5 to 60% by mass and preferably 15 to 40% by mass with respect to the total solid content of the colored photosensitive resin composition (i). C. above. I. P. R. If the content of 177 is less than 5% by mass, the color may be light, and if it exceeds 60% by mass, it may be difficult to adjust various performances such as developability.
C. above. I. P. R. 254 and the C.I. I. P. R. 177 may be used in combination.

C. above. I. P. G. The content of 36 is preferably 5 to 60% by mass, and preferably 25 to 45% by mass, based on the total solid content of the colored photosensitive resin composition (ii). C. above. I. P. G. If the content of 36 is less than 5% by mass, the color may be thin, and if it exceeds 60% by mass, it may be difficult to adjust various performances such as developability.
C. above. I. P. Y. The content of 150 is preferably 1 to 20% by mass, and preferably 5 to 15% by mass, based on the total solid content of the colored photosensitive resin composition (ii). C. above. I. P. Y. If the content of 150 is less than 1% by mass, the effect may be reduced, and if it exceeds 20% by mass, it may be difficult to adjust the hue.
C. above. I. P. Y. The content of 138 is preferably 1 to 20% by mass, and preferably 5 to 15% by mass, based on the total solid content of the colored photosensitive resin composition (ii). C. above. I. P. Y. If the content of 138 is less than 1% by mass, the effect may be less manifested, and if it exceeds 20% by mass, hue adjustment may be difficult.

C. above. I. P. B. The content of 15: 6 is preferably 5 to 60% by mass and preferably 15 to 25% by mass with respect to the total solid content of the colored photosensitive resin composition (iii). C. above. I. P. B. When the content of 15: 6 is less than 5% by mass, the color may be thin, and when it exceeds 60% by mass, it may be difficult to adjust various performances such as developability.
C. above. I. P. V. The content of 23 is preferably 0.1 to 10% by mass, and preferably 0.5 to 3% by mass, based on the total solid content of the colored photosensitive resin composition (iii). C. above. I. P. V. If the content of 23 is less than 0.1% by mass, the effect may be reduced, and if it exceeds 10% by mass, hue adjustment may be difficult.

Examples of the black pigment in the colored photosensitive resin composition (iv) include carbon black.
The black pigment content is preferably 5 to 60% by mass with respect to the total solid content of the colored photosensitive resin composition (iv). When the content of the black pigment is 25 to 55% by mass, the color may be thin when it is less than 5% by mass, and when it exceeds 60% by mass, it is difficult to adjust various properties such as developability. There is.
There are things to do.

These colorants are desirably used as dispersions. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later.
The vehicle refers to a portion of the medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), which is dissolved and diluted. Component (organic solvent).
The disperser used when dispersing the pigment is not particularly limited, and examples thereof include known dispersers such as a kneader, a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill.
The pigment dispersant is not particularly limited and may be appropriately selected from known ones. For example, JP-A 2000-239554, 2003-96329, 2001-31885, JP Examples thereof include, but are not limited to, compounds described in JP-A-10-339949 and JP-B-5-72943.

  The number average particle diameter of the colorant is, for example, preferably 0.2 μm or less, and more preferably 0.01 to 0.1 μm. When the particle shape is 0.2 μm or more, the contrast may be lowered.

<Other ingredients>
Examples of the other components include solvents, surfactants, thermal polymerization inhibitors, auxiliary dyes and pigments, ultraviolet absorbers, and the like.

-Solvent-
In the colored photosensitive resin composition of this invention, a solvent can be included as needed.
Examples of the solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, and the like.

-Surfactant-
Conventionally used color filters have a problem that the color of each pixel becomes dark in order to realize high color purity, and the uneven thickness of the pixel is recognized as the color unevenness as it is. For this reason, it has been desired to improve the thickness variation during the formation (application) of the photosensitive resin layer, which directly affects the pixel thickness.
In the color filter of the present invention or the photosensitive resin transfer material of the present invention, the colored photosensitive resin composition can be controlled to have a uniform thickness and effectively prevent coating unevenness (color unevenness due to thickness variation). It is preferable to contain an appropriate surfactant therein.
As the surfactant, for example, surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600 are preferable.

-Thermal polymerization inhibitor-
The colored photosensitive resin composition of the present invention can contain a thermal polymerization inhibitor, if necessary.
Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

-Supplementary dyes and pigments-
In the colored photosensitive resin composition of the present invention, in addition to the colorant (pigment) as needed, dyes and pigments (known colorants) to be used in an auxiliary manner as long as the effects of the present invention are not impaired. Can be included.
When using a pigment among the known colorants, it is desirable that the pigment is uniformly dispersed in the colored photosensitive resin composition. Therefore, the particle size of the known colorant is, for example, preferably 0.1 μm or less, and more preferably 0.08 μm or less.
Specific examples of the known colorant include, for example, coloring materials described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. And pigments described in JP-A-2005-17521 [0080] to [0088] are preferable.

-UV absorber-
The colored photosensitive resin composition of the present invention can contain an ultraviolet absorber as necessary.
Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724. .
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebakei 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl ) -Ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine- 2-yl] amino} -3-phenylcoumarin, and the like.

  Further, in the colored photosensitive resin composition of the present invention, if necessary, in addition to the other additives, for example, “adhesion aid” described in JP-A-11-133600, other Additives and the like can be included.

(Photosensitive resin transfer material)
The photosensitive resin transfer material of the present invention includes a temporary support and a photosensitive resin layer, and includes other components as necessary.
The photosensitive resin transfer material of the present invention is characterized in that the photosensitive resin layer is provided by using the colored photosensitive resin composition of the present invention.
In the photosensitive resin transfer material of the present invention, the photosensitive resin layer is made of the colored photosensitive resin composition of the present invention, so that the curing sensitivity is high and the film thickness can be made uniform.

The photosensitive resin transfer material of the present invention is preferably a photosensitive resin transfer material described in JP-A-5-72724, that is, an integral film.
Examples of the structure of the integral film include a structure in which a temporary support, a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer, and a protective film are laminated in this order.

<Photosensitive resin layer>
The photosensitive resin layer of the present invention includes at least a binder, a polymerizable compound, a photopolymerization initiator, and a colorant, and if necessary, the colored photosensitive property of the present invention including other components. A coating film of a resin composition, wherein the compound represented by the general formula (1) is used as the photopolymerization initiator.
The binder, polymerizable compound, photopolymerization initiator, colorant, and other components are the same as those described in the description of the colored photosensitive resin composition.

The photosensitive resin layer can be formed by applying and drying the colored photosensitive resin composition of the present invention by a known application method. For example, the photosensitive resin layer has a slit-like hole in a portion from which the liquid is discharged. It is preferable to apply by a slit nozzle.
Specific examples of the slit-shaped nozzle include, for example, Japanese Patent Application Laid-Open Nos. 2004-89851, 2004-17043, 2003-170098, 2003-164787, and 2003-10767. Slit nozzles and slit coaters described in JP-A-2002-79163, JP-A-2001-310147 and the like are preferable.

<Temporary support>
The temporary support is required to be flexible and not to be significantly deformed, contracted or stretched either under pressure or under heating.
Examples of the temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a biaxially stretched polyethylene terephthalate film is preferable.

<Thermoplastic resin layer>
The component used for the thermoplastic resin layer is preferably an organic polymer substance described in JP-A-5-72724, and polymer softening by the Viker Vicat method (specifically, American Material Testing Method ASTM D1 ASTM D1235). An organic polymer substance having a softening point of about 80 ° C. or less by a point measurement method is more preferable.
Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkyloxy Methylated nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

<Intermediate layer>
In the photosensitive resin transfer material of the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application.
As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. When the intermediate layer is present, the sensitivity at the time of exposure is increased, the time load of the exposure machine is reduced, and the productivity is improved.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkaline solution, and can be appropriately selected from known ones, but a combination of polyvinyl alcohol and polyvinyl pyrrolidone Is preferred.

<Protective film>
A thin protective film is preferably provided on the photosensitive resin layer in order to protect it from contamination and damage during storage.
The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer.
As the material for the protective film, for example, silicone paper, polyolefin, and polytetrafluoroethylene sheet are preferable.

-Preparation method of photosensitive resin transfer material-
Examples of the method for producing the photosensitive resin transfer material of the present invention include the following methods. For example, a thermoplastic resin layer is provided by applying a coating solution (a coating solution for a thermoplastic resin layer) in which an additive for a thermoplastic resin layer is dissolved on a temporary support, followed by drying. Next, a solution of the intermediate layer material (intermediate layer coating solution) composed of a solvent that does not dissolve the thermoplastic resin layer is applied onto the thermoplastic resin layer and dried to provide the intermediate layer. Next, the photosensitive resin layer material solution (coating solution for the photosensitive resin layer) composed of a solvent that does not dissolve the intermediate layer is applied onto the intermediate layer, dried, and a photosensitive resin layer is provided. can do.
In addition, a sheet provided with a thermoplastic resin layer and an intermediate layer on the temporary support, and a sheet provided with a photosensitive resin layer on a protective film are prepared so that the intermediate layer and the photosensitive resin layer are in contact with each other. It can also be produced by sticking together.
Also, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive resin layer and an intermediate layer on a protective film are prepared so that the thermoplastic resin layer and the intermediate layer are in contact with each other. It can also be produced by sticking together.
The thickness of the photosensitive resin layer is preferably 1.0 to 5.0 μm, more preferably 1.0 to 4.0 μm, and particularly preferably 1.0 to 3.0 μm. If the thickness is 1.0 μm or less, sufficient coloring may not be obtained.
The thickness of each of the other layers is not particularly limited and may be appropriately selected. For example, the temporary support is 15 to 100 μm, the thermoplastic resin layer is 2 to 30 μm, and the intermediate layer is 0.5 to 3.0 μm. The protective film is preferably 4 to 40 μm.

The coating method in the production method can be performed by a known coating apparatus or the like, but is preferably performed by a coating apparatus (slit coater) using the slit-shaped nozzle described in the photosensitive resin layer.
Specific examples of the slit coater include those similar to the specific examples of the slit nozzle.

(Color filter)
The color filter of the present invention includes a photosensitive resin layer and a substrate, and includes other layers as necessary.
The color filter of the present invention has a photosensitive resin layer formed by using the colored photosensitive resin composition of the present invention or the photosensitive resin transfer material of the present invention, so that the curing sensitivity is high and preferable chromaticity. A color filter having the following can be manufactured.

<Photosensitive resin layer>
The photosensitive resin layer is formed using the colored photosensitive resin composition of the present invention or the photosensitive resin transfer material of the present invention.
The photosensitive resin layer in the color filter of the present invention is preferably composed of a red (R) photosensitive resin layer, a green (G) photosensitive resin layer, and a blue (B) photosensitive resin layer. If necessary, it is preferable to include a black matrix photosensitive resin layer.
The red (R) photosensitive resin layer contains C.I. I. P. R. 254 and C.I. I. P. R. It is preferable that it consists of the said colored photosensitive resin composition using any of 177.
The green (G) photosensitive resin layer contains C.I. I. P. G. 36, C.I. I. P. Y. 150, and C.I. I. P. Y. It is preferable that it consists of the said coloring photosensitive resin composition using any of 138.
The blue (B) photosensitive resin layer contains C.I. I. P. B. 15: 6 and C.I. I. P. V. It is preferable to consist of the said colored photosensitive resin composition using any of 23.
The black matrix photosensitive resin layer is preferably made of a colored photosensitive resin composition using a black pigment as a colorant.
When the photosensitive resin layer in the color filter of the present invention satisfies the above requirements, it has a good chromaticity in the F10 light source field of view of 2 degrees, and even when used in a liquid crystal display device or the like, it has a high color purity. Can be realized.

  In the color filter of the present invention, the chromaticities of all single colors of red (R), green (G), and blue (B) by the F10 light source are the values described in Table 1 below (hereinafter referred to as the present invention). The difference (ΔE) from the “target chromaticity” is preferably within 5 ranges, more preferably within 3 ranges, and particularly preferably within 2 ranges.

Here, in the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. Further, the difference from the target chromaticity is represented by a color difference of the La ^* b ^* color system.

(substrate)
Examples of the substrate include a transparent glass substrate, a soda glass plate having a silicon oxide film on its surface, a low-expansion glass, a non-alkali glass, a known glass plate such as a quartz glass plate, or a plastic film. Can do.
The substrate is preferably subjected to a coupling process in advance. By subjecting the substrate to a coupling treatment, adhesion to the colored photosensitive resin composition or the photosensitive resin transfer material can be improved.
As the coupling treatment, for example, a method described in JP 2000-39033 A is preferable.
There is no restriction | limiting in particular as thickness of the said board | substrate, It can select suitably, For example, 700-1200 micrometers is preferable.

<Other layers>
Examples of the other layers include an oxygen barrier film, a release layer, an adhesive layer, a light absorption layer, and a surface protective layer.

-Oxygen barrier film-
In the color filter of the present invention, an oxygen blocking film can be provided as necessary. In the case where the photosensitive resin layer is formed by application of a colored photosensitive resin composition, an oxygen-blocking film can be further provided on the photosensitive resin layer, thereby increasing the exposure sensitivity.
Examples of the oxygen blocking film include those similar to the intermediate layer in the description of the photosensitive resin transfer material.
There is no restriction | limiting in particular in the thickness of the said oxygen interruption | blocking film | membrane, It can select suitably, For example, 0.5-3.0 micrometers is preferable.

-Color filter manufacturing method-
The method for producing a color filter of the present invention includes a photosensitive resin layer forming step, an exposure step, a developing step, a curing step, and other steps as necessary.
In the photosensitive resin layer forming step, a photosensitive resin layer is formed using the colored photosensitive resin composition or the photosensitive resin transfer material.
Since the manufacturing method of the color filter of the present invention includes the photosensitive resin layer forming step, the exposure step, the developing step, and the curing step, the pattern can be formed with high definition and efficiency. It can be suitably used for the formation of various patterns that require fine exposure, and can be particularly suitably used for the formation of high-definition color filter patterns.
The color filter of the present invention can be produced by a known method such as a method in which a photosensitive resin layer is formed on a substrate, and exposure and development are repeated for the number of colors. If necessary, the boundary may be divided by a black matrix.

--Photosensitive resin layer forming process--
The photosensitive resin layer forming step is a step of forming at least a photosensitive resin layer on the surface of the substrate using the colored photosensitive resin composition and further forming other appropriately selected layers.

There is no restriction | limiting in particular as a method of forming the said photosensitive resin layer and other layers, According to the objective, it can select suitably, For example, the method of forming by application | coating, pressurizing and heating each sheet-like layer The method of forming by laminating by performing at least one of these, combined use, etc. are mentioned.
Suitable examples of the photosensitive resin layer forming step include the photosensitive resin layer forming step of the first aspect and the photosensitive resin layer forming step of the second aspect described below.

  As the photosensitive resin layer forming step of the first aspect, at least a photosensitive resin layer is formed on the surface of the substrate by applying the colored photosensitive resin composition to the surface of the substrate and drying. Furthermore, there is a step of forming other layers appropriately selected.

  In the photosensitive resin layer forming step of the second aspect, the photosensitive resin transfer material obtained by forming the colored photosensitive resin composition into a film is laminated on the surface of the substrate under at least one of heating and pressing. By doing, the process of forming at least the photosensitive resin layer on the surface of a base material, and also forming the other layer selected suitably is mentioned.

  In the photosensitive resin layer forming step of the first aspect, the coating and drying method is not particularly limited and can be appropriately selected depending on the purpose. For example, the colored photosensitive layer is formed on the surface of the substrate. And a method of laminating the photosensitive resin composition by dissolving, emulsifying or dispersing it in water or a solvent to prepare a colored photosensitive resin composition solution, directly applying the solution, and drying the solution.

  There is no restriction | limiting in particular as a solvent of the said colored photosensitive resin composition solution, According to the objective, it can select suitably.

The coating method is not particularly limited and can be appropriately selected depending on the purpose. For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. The method of apply | coating is mentioned. In this invention, it is preferable to carry out by the coating device (slit coater) using the slit-shaped nozzle which has a slit-shaped hole in the part which discharges a liquid.
Among these, specific examples of the slit coater include those similar to the slit coater described in the photosensitive resin layer.
When the photosensitive resin layer is formed by coating, the thickness of the photosensitive resin layer is preferably 1.0 to 3.0 μm, more preferably 1.0 to 2.5 μm, and 1.0 to 2.0 μm. Is particularly preferred.

  The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually 60 to 110 ° C. and about 30 seconds to 15 minutes.

There is no restriction | limiting in particular as another layer formed in the photosensitive resin layer formation process of a 1st aspect, According to the objective, it can select suitably, For example, an oxygen interruption | blocking layer, a peeling layer, an adhesive layer, light An absorption layer, a surface protective layer, etc. are mentioned.
There is no restriction | limiting in particular as a formation method of the said other layer, According to the objective, it can select suitably, For example, the method of apply | coating on the said photosensitive resin layer, lamination | stacking the other layer formed in the sheet form The method of doing is mentioned.

In the photosensitive resin layer forming step of the second aspect, as a method of forming the photosensitive resin layer on the surface of the base material and other layers appropriately selected as necessary, a temporary provision is made on the surface of the base material. Heating and pressurizing a photosensitive resin transfer material having a support, a photosensitive resin layer in which a colored photosensitive resin composition is laminated on the temporary support, and other layers appropriately selected as necessary And a method of laminating while performing at least one of the following: a photosensitive resin transfer material in which a colored photosensitive resin composition is laminated on a temporary support, and the colored photosensitive resin composition is on the surface side of the substrate The method of laminating | stacking so that it may become, and then peeling a temporary support body from the colored photosensitive resin composition is mentioned suitably.
By peeling off the support, it is possible to prevent a blurred image from being formed on the image formed on the colored photosensitive resin composition layer due to light scattering or refraction by the support, and to increase the predetermined pattern. Obtained with resolution.
In addition, when the said photosensitive resin transfer material has a protective film mentioned later, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive resin layer may overlap with the said base material.

There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 70-130 degreeC is preferable and 80-110 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.

There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, heat press, a heat roll laminator (For example, Taisei Laminator Co., Ltd. make, VP -II), a vacuum laminator (for example, MVLP500 manufactured by Meiki Seisakusho) and the like are preferable.
Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794.
Among these, it is preferable to use the method described in JP-A-7-110575 from the viewpoint of low foreign matter.
When the photosensitive resin layer is formed of the photosensitive resin transfer material of the present invention, the thickness of the photosensitive resin layer is the same as the thickness of the photosensitive resin layer described in the section of the photosensitive resin transfer material. is there.

--Exposure process--
Examples of the exposure include exposure using a mask on the photosensitive resin transfer material.
There is no restriction | limiting in particular as exposure using the said mask, According to the objective, it can select suitably, For example, after arrange | positioning a predetermined mask above the photosensitive resin layer etc. which were formed on the said board | substrate, There are a method of exposing from above the mask through the mask, a photosensitive resin layer and the like, and a method of exposing directly with leather.
Here, as the light source for exposure, any light source capable of irradiating light in a wavelength region capable of curing the resin layer (for example, 365 nm, 405 nm, etc.) can be appropriately selected and used. Specific examples include ultra high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, semiconductor lasers, and light emitting diodes.
As the exposure amount, for example, it is preferably 0.1~200mJ / cm ^2, more preferably 0.1~100mJ / cm ^2.

--Development process--
The developing step is a step of developing the photosensitive layer by exposing the photosensitive layer by the exposing step and removing an unexposed portion.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

There is no restriction | limiting in particular as said developing solution, It can select suitably from well-known things, For example, what is described in Unexamined-Japanese-Patent No. 5-72724 etc. is mentioned.
The developer is preferably one in which the photosensitive resin layer exhibits a dissolution type development behavior.
As the developer, for example, a developer containing a compound having pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. Furthermore, a small amount of an organic solvent miscible with water may be added.
Examples of the organic solvent miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether. Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone, etc. .
As a density | concentration of the said organic solvent, 0.1-30 mass% is preferable, for example.
A known surfactant can be further added to the developer.
The concentration of the surfactant is preferably 0.01 to 10% by mass.

There is no restriction | limiting in particular as said image development system, It can select suitably from well-known things, For example, a paddle image development, shower image development, shower & spin image development, dip image development, etc. are mentioned.
Here, the shower development will be described. In the shower development, an uncured portion can be removed by spraying a developer onto the photosensitive resin layer after exposure.
In addition, it is preferable to spray an alkaline liquid with low solubility of the photosensitive resin layer by a shower or the like before development to remove the thermoplastic resin layer, the intermediate layer, and the like.
Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., for example.
The pH value of the developer is preferably 8 to 13, for example.

--Curing process--
It is a step of performing a curing treatment on the photosensitive resin layer after the developing step.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the pattern is formed after the developing step. The entire surface exposure accelerates the curing of the resin in the colored photosensitive resin composition forming the photosensitive layer, and the surface of the pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the pattern is formed after the developing step. The whole surface heating increases the film strength of the surface of the pattern.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the colored photosensitive resin composition is decomposed and the film quality is weak. May become brittle.
As heating time in the said whole surface heating, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

-Other processes-
There is no restriction | limiting in particular as said other process, Although selecting suitably from the process in well-known pattern formation is mentioned, For example, a thermosetting process, a photocuring process, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

In the color filter manufacturing method of the present invention, as described above, the pixels of the three primary colors RGB can be arranged in a mosaic or stripe pattern on a transparent substrate such as a glass substrate by the pattern forming method of the present invention. .
There is no restriction | limiting in particular as a dimension of each pixel, According to the objective, it can select suitably, For example, it is preferable to set it as 40-200 micrometers. In the case of a stripe shape, the width is preferably 40 to 200 μm.
As the color filter manufacturing method, for example, a photosensitive layer colored in black on a transparent substrate is used to perform exposure and development to form a black matrix, and then a photosensitive color that is colored in one of the three primary colors RGB. A color filter in which three primary colors of RGB are arranged in a mosaic or stripe pattern on the transparent substrate by repeating exposure and development for each color in a predetermined arrangement with respect to the black matrix using a layer. The method of forming is mentioned.

In the production of the color filter of the present invention, as described in JP-A Nos. 11-248921 and 3255107, a colored photosensitive resin composition for forming a color filter is overlaid to form a base, It is preferable from the viewpoint of cost reduction that the transparent electrode is formed on the spacer and the spacers are further formed by overlapping the protrusions for split orientation.
When the colored photosensitive resin composition is sequentially applied and stacked, the thickness decreases as the layers are stacked due to the leveling of the coating solution. For this reason, it is preferable to overlap the four colors of K (black), R, G, and B and further overlap the divisional alignment protrusions.
In the case of using a transfer material having the thermoplastic resin layer, it is preferable that three or two colors be superimposed because the thickness is kept constant.
The thickness (size) of the cushion layer (base) is preferably 25 μm or more, and particularly preferably 30 μm or more, from the viewpoint of preventing deformation of the photosensitive resin layer and maintaining a certain thickness when the transfer material is laminated and laminated.

(Liquid crystal display device)
The liquid crystal display device of the present invention comprises a liquid crystal sealed between a pair of substrates arranged opposite to each other, has the color filter of the present invention, and further has other members as necessary. It becomes.
The color filter of the present invention is intended to be formed on the counter substrate of the liquid crystal display device (the substrate on the side where there is no active element such as a TFT). The BOA method for forming the layer or the HA method having a high aperture structure on the TFT substrate can also be targeted.

  An overcoat film or a transparent conductive film can be further formed on the color filter as necessary. Thereafter, liquid crystal is sealed between the color filter and the counter substrate, and a liquid crystal display device is manufactured. The liquid crystal display method is not particularly limited and is appropriately selected according to the purpose. For example, TN, STN (super twisted nematic), IPS (in-plane switching), GH (guest host) , FLLC (ferroelectric liquid crystal), AFLC (antiferroelectric liquid crystal), PDLC (polymer dispersion type liquid crystal) and the like.

  The basic configuration of the liquid crystal display device includes: (1) a driving side substrate in which driving elements such as thin film transistors (hereinafter referred to as “TFTs”) and pixel electrodes (conductive layers) are arrayed, and a color filter. And a color filter side substrate provided with a counter electrode (conductive layer) opposite to each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap, and (2) the color filter is disposed on the drive side substrate. Directly formed color filter integrated drive substrate and counter substrate having a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap portion. It is done.

  In addition, the liquid crystal display device of the present invention can achieve high color purity and color temperature by using the color filter of the present invention having good chromaticity in the F10 light source field of view of 2 degrees. The liquid crystal display device can be suitably used.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to these Examples. Unless otherwise specified, “parts”, “%” and “molecular weight” represent “parts by mass”, “mass%” and “weight average molecular weight”, respectively.

Example 1
[Preparation of color filter (preparation by application using slit nozzle)]
-Formation of black (K) image-
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the composition described in Table 2 below is applied on a glass substrate coater (manufactured by FS Japan, trade name: MH-1600) having a slit-like nozzle. The following colored photosensitive resin composition K1 was applied. Subsequently, after a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, the periphery of the substrate was surrounded by EBR (edge bead remover). Unnecessary coating solution was removed and prebaked at 120 ° C. for 3 minutes to obtain a photosensitive resin layer K1 having a thickness of 1.6 μm.

In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface and the photosensitive film The distance between the conductive resin layers was set to 200 μm, and pattern exposure was performed with an exposure amount of 300 mJ / cm ² .

  Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, Fujifilm Electronics Materials) performed shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image was obtained. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

-Formation of red (R) pixels-
Using the following colored photosensitive resin composition R1 having the composition shown in Table 3 on the substrate on which the K image is formed, heat-treated R pixels are formed in the same process as the black (K) image formation. did.
Table 6 shows the thickness of the photosensitive resin layer R1 and the coating amounts of the pigments (CIPR 254 and CIPR 177).

-Formation of green (G) pixels-
Using the following colored photosensitive resin composition G1 having the composition shown in Table 4 below on the substrate on which the K image and R pixel are formed, heat treatment is performed in the same process as the formation of the black (K) image. G pixels were formed.
Table 6 shows the thickness of the photosensitive resin layer G1 and the coating amounts of the pigments (CIPG36 and CIPY150).

-Formation of blue (B) pixels-
In the same process as the formation of the black (K) image, using the following colored photosensitive resin composition B1 having the composition shown in Table 5 below on the substrate on which the K image, R and G pixels are formed. Heat-treated B pixels were formed to obtain the target color filter.
Table 6 shows the thickness of the photosensitive resin layer B1 and the coating amounts of the pigments (CIPB15: 6 and CIPVV23).

Here, preparation of the colored photosensitive resin compositions K1, R1, G1, and B1 described in Tables 2 to 5 will be described.
The colored photosensitive resin composition K1 is first weighed in the amount of K pigment dispersion 1 and propylene glycol monomethyl ether acetate listed in Table 2, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 RPM for 10 minutes, and then The amounts of methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, compound 1 and surfactant 1 in the amounts shown in Table 2 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.), and a temperature of 40 ° C. ( It was obtained by stirring at 150 RPM for 30 minutes at ± 2 ° C.

In addition, the composition of K pigment dispersion 1 is shown as follows among the compositions of Table 2.
-Composition of K pigment dispersion 1-
・ Carbon black (trade name: Nippon 35, manufacturer: Degussa Japan Co., Ltd.) ... 13.1 parts, dispersant (compound represented by the following structural formula (1)) ... 0.65 parts, polymer (benzyl methacrylate / methacrylic acid) = Random copolymer with a molar ratio of 72/28, molecular weight 37,000) ... 6.72 parts, propylene glycol monomethyl Ether acetate ... 79.53 parts

The composition of the binder 2 is shown as follows.
-Composition of binder 2-
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ 27 parts ・ Propylene glycol monomethyl ether acetate …… 73 parts

The composition of the DPHA liquid is shown by the following composition.
-Composition of DPHA solution-
・ Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) ・ ・ ・ ・ ・ ・ 76 parts ・ Propylene glycol monomethyl ether acetate ・ ・ ・ ・.... 24 parts

The composition of the surfactant 1 is shown as follows.
-Composition of surfactant 1-
・ Compound represented by the following structural formula (2) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 30 parts ・ Methyl ethyl ketone ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・.... 70 parts

  The colored photosensitive resin composition R1 was first weighed in the amounts of R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate shown in Table 3, and mixed at a temperature of 24 ° C. (± 2 ° C.). Stir at 150 RPM for 10 minutes, then weigh out the amounts of methyl ethyl ketone, binder 1, DPHA solution, compound 1 (specific example of the photopolymerization initiator) and phenothiazine shown in Table 3 at a temperature of 24 ° C. (± 2 ° C.). Add in this order and stir at 150 RPM for 30 minutes, then weigh out the amount of Surfactant 1 listed in Table 3, add it at a temperature of 24 ° C. (± 2 ° C.), stir at 30 RPM for 5 minutes, and filter with nylon mesh # 200 Was obtained by

In addition, the composition of R pigment dispersion 1 among the compositions of Table 3 is shown as follows.
-Composition of R pigment dispersion 1-
・ C. I. P. R. 254 (trade name: Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 8 parts ・ Dispersant (the above structure) Compound represented by formula (1)) ... 0.8 parts Polymer (Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 30,000 ) ... 8 partsPropylene glycol monomethyl ether acetate ... 83 parts

The composition of the R pigment dispersion 2 is shown as follows.
-Composition of R pigment dispersion 2-
・ C. I. P. R. 177 (trade name: Chromophthal Red A2B, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 18 parts Polymer (benzyl methacrylate / methacrylic acid = 72) / Random copolymer of 28 molar ratio, molecular weight 30,000) ... 12 parts, propylene glycol monomethyl ether acetate ... 70 parts

The composition of the binder 1 is shown as follows.
-Binder 1
・ Polymer (Random copolymer of benzyl methacrylate / methacrylic acid / methyl methacrylate = 38/25/37 molar ratio, molecular weight 40,000) ... 27 parts ・ Propylene glycol monomethyl ether acetate .... 73 parts

  The colored photosensitive resin composition G1 was first weighed in the amounts of G pigment dispersion 1, Y pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts shown in Table 4, and mixed at a temperature of 24 ° C. (± 2 ° C.). The mixture was stirred at 150 RPM for 10 minutes, and then the amounts of methyl ethyl ketone, cyclohexanone, binder 2, DPHA solution, compound 1 (specific example of the photopolymerization initiator) and phenothiazine in the amounts shown in Table 4 were weighed and the temperature was 24 ° C. (± 2 ° C. ) In this order and stirred at 150 RPM for 30 minutes. Further, the amount of surfactant 1 listed in Table 4 was weighed out, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 RPM for 5 minutes, and nylon mesh # 200. It was obtained by filtering through.

In addition, among the compositions described in Table 4, “trade name: GT-2” manufactured by FUJIFILM Electronics Materials Co., Ltd. was used as the G pigment dispersion 1.
As the Y pigment dispersion 1, “trade name: CF Yellow EX3393” manufactured by Mikuni Color Co., Ltd. was used.

  The colored photosensitive resin composition B1 is first weighed in the amounts of B pigment dispersion 1, B pigment dispersion 2, and propylene glycol monomethyl ether acetate shown in Table 5 and mixed at a temperature of 24 ° C. (± 2 ° C.). Stir at 150 RPM for 10 minutes, then weigh out the amounts of methyl ethyl ketone, binder 3, DPHA solution, compound 1 (specific example of the photopolymerization initiator) and phenothiazine shown in Table 5 at a temperature of 25 ° C. (± 2 ° C.). Add in this order, stir at a temperature of 40 ° C. (± 2 ° C.) for 150 RPM for 30 minutes, and then weigh out the amount of surfactant 1 listed in Table 5 and add at a temperature of 24 ° C. (± 2 ° C.) at 30 RPM 5 It is obtained by stirring for minutes and filtering through nylon mesh # 200.

Of the compositions listed in Table 5,
As the B pigment dispersion 1, “trade name: CF Blue EX3357” manufactured by Mikuni Color Co., Ltd. was used.
As the B pigment dispersion 2, “trade name: CF Blue EX3383” manufactured by Mikuni Dye Co., Ltd. was used.

The composition of the binder 3 is shown as follows.
-Binder 3-
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 27 parts ・ Propylene glycol monomethyl ether acetate .... 73 parts

[Evaluation]
-Measurement of chromaticity-
The chromaticity of the color filter obtained from the above was measured at a pinhole diameter of 5 μm using a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100), and calculated as a result of the F10 light source field of view of 2 degrees. The results (xyY values) are shown in Table 6.

-Coating unevenness-
The substrate immediately after the application of the colored photosensitive resin compositions of R, G, and B colors was irradiated with a Na lamp from an oblique direction in a dark room, and observed visually and with a magnifying glass to determine whether or not unevenness had occurred.

-Display unevenness-
The substrate with pixels for which patterning was completed was irradiated with a Na lamp from an oblique direction in a dark room and observed visually and with a magnifying glass to determine whether or not unevenness had occurred.

-Exposure sensitivity-
Exposure using the exposure mask of the pattern width 25 [mu] m (actual width 25 [mu] m transparent portion), development, performs residue removal, the line width of the resulting image is displayed with a exposure amount becomes 25μm (mJ / cm ²⁾ . That is, a resist with a small exposure amount has high sensitivity because an image can be formed with a low exposure amount.

-Resolution-
The minimum resist pattern size that can be resolved at the appropriate exposure light amount obtained by the exposure sensitivity was evaluated according to the following criteria.
<Standard>
A: The minimum pattern dimension is 10 μm or less.
(Triangle | delta): The minimum pattern dimension exceeds 10 micrometers and is 15 micrometers or less.
X: The minimum pattern dimension exceeds 15 μm.

(Example 2)
In Example 1, the photopolymerization initiator used in the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1 is used as the compound. A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 11 was changed from 1 to 11, and the colored photosensitive resin composition K2, the colored photosensitive resin composition R2, and the colored photosensitive resin composition were prepared. The product G2 and the colored photosensitive resin composition B2 were obtained, color filters were produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

(Example 3)
In Example 1, the photopolymerization initiator used in the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1 is used as the compound. A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 15 was changed from 1 to the compound 15, and the colored photosensitive resin composition K3, the colored photosensitive resin composition R3, and the colored photosensitive resin composition were prepared. Product G3 and colored photosensitive resin composition B3 were obtained, color filters were produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

Example 4
In Example 1, the photopolymerization initiator used in the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1 is used as the compound. A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 16 was changed from 1 to the compound 16, and the colored photosensitive resin composition K4, the colored photosensitive resin composition R4, and the colored photosensitive resin composition were prepared. Product G4 and colored photosensitive resin composition B4 were obtained, color filters were produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

(Example 5)
In Example 1, the photopolymerization initiator used for the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1, A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound 17 was changed, and the colored photosensitive resin composition K5, the colored photosensitive resin composition R5, and the colored photosensitive resin composition G5. And the color photosensitive resin composition B5 was obtained, the color filter was produced by the method similar to Example 1, and it evaluated similarly to Example 1. FIG.

(Comparative Example 1)
In Example 1, the photopolymerization initiator used for the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1 is obtained from the compound 1. A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that it was changed to CGI-242 (manufactured by Ciba Specialty Chemicals), and colored photosensitive resin composition K101 and colored photosensitive resin composition R101. A colored photosensitive resin composition G101 and a colored photosensitive resin composition B101 were obtained, color filters were produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

(Comparative Example 2)
The photopolymerization initiator used in the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1 in Example 1 is obtained from the compound 1. A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that it was changed to CGI-OXE01 (manufactured by Ciba Specialty Chemicals), and the colored photosensitive resin composition K102 and colored photosensitive resin composition R102 were prepared. A colored photosensitive resin composition G102 and a colored photosensitive resin composition B102 were obtained, color filters were produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1.

* 1: Thickness indicates the thickness of the photosensitive resin layer formed on the substrate before exposure.

[Production and Evaluation of Liquid Crystal Display]
Resin spacers were formed on the pixels of the color filters of Examples 1 to 5 and Comparative Examples 1 and 2 by the same method as in Example 1 of JP-A-2003-207787.
Next, a transparent electrode layer of ITO (Indium Tin Oxide) was formed and patterned for the PVA mode.
Further, a polyimide alignment film was provided on the patterned transparent electrode layer. After applying an epoxy resin sealing material at a position corresponding to the outer frame of the black matrix provided around the pixel group of the color filter, dropping the liquid crystal for PVA mode in a vacuum and superposing it on the counter substrate, It returned to atmospheric pressure and bonded together by pressurization by atmospheric pressure to obtain a liquid crystal cell.
Next, the bonded substrate was subjected to ultraviolet treatment to cure the sealing material.
A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both sides of the liquid crystal cell so as to be crossed Nicol. Next, FR1112H (chip type LED manufactured by Stanley Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Co., Ltd.) as a green (G) LED, and DB1112H (chip manufactured by Stanley Co., Ltd.) as a blue (B) LED A side-light type backlight was constructed using a type LED) and placed on the back side of the liquid crystal cell provided with the polarizing plate to produce a liquid crystal display device having a screen size of 25 inches.
It was confirmed that the liquid crystal display device using the color filter of the example showed better display characteristics than the liquid crystal display device using the color filter of the comparative example.

(Example 6)
[Production of color filter (production by lamination of photosensitive resin transfer material)]
-Production of photosensitive resin transfer material-
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, the colored photosensitive resin composition K1 is applied and dried, and a thermoplastic resin layer having a dry thickness of 14.6 μm, an intermediate layer having a dry thickness of 1.6 μm, and a dry thickness on the temporary support. A 2.0 μm photosensitive resin layer was provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded.
In this way, a photosensitive resin transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer are integrated is prepared, and the sample name is the photosensitive resin transfer material. It was set as K1.

Coating liquid for thermoplastic resin layer: Formulation H1
· Methanol ···························································· Propylene glycol monomethyl ether acetate ······ 6.36 parts · Methyl ethyl ketone · ··········································· 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio)) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 90,000, Tg≈70 ° C.) 5.83 parts styrene / acrylic Acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, molecular weight = 10,000, Tg≈100 ° C.) .2 parts ・ 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate Water-condensed compound (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane) ...・ ・ ・ 9.1 parts ・ Surfactant 1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.54 parts

Intermediate layer coating solution: Formulation P1
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550)・ 32.2 parts ・ Polyvinylpyrrolidone (manufactured by IPS Japan Co., Ltd., K-30)
・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 14.9 parts ・ Distilled water ...・ ・ ・ ・ ・ 524 parts ・ Methanol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 429 parts

Next, the colored photosensitive resin composition K1 used in the production of the photosensitive resin transfer material K1 is changed to the colored photosensitive resin composition R1, G1, and B1, and the other methods are the same as described above. Photosensitive resin transfer materials R1, G1, and B1 were produced.
In addition, the preparation method of colored photosensitive resin composition R1, G1, and B1 is based on the preparation method of the said colored photosensitive resin composition R1, G1, and B1, respectively.

-Formation of black (K) image-
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. The substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device and sent to the next laminator.
After peeling off the protective film of the photosensitive resin transfer material K1, a substrate heated to 100 ° C. using a laminator (manufactured by Hitachi Industries (Lamic II type)), rubber roller temperature 130 ° C., linear pressure 100N / Cm ² and laminate at a conveying speed of 2.2 m / min.
After the temporary support is peeled off at the interface with the thermoplastic resin layer, the substrate and mask (quartz exposure mask with image pattern) are mounted on a proximity-type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. While standing upright, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

Next, at 30 ° C. for 50 seconds in a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, Fuji Photo Film) Then, shower development was performed at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer.
Subsequently, a sodium carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T -CD1, manufactured by Fuji Photo Film Co., Ltd.), shower development was performed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa, and the photosensitive resin layer was developed to obtain a patterned image.
Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name “T-SD1 (Fuji Photo Film Co., Ltd.)”), cone type nozzle pressure at 33 ° C. for 20 seconds. Residue removal was performed with a rotating brush having a shower and nylon hair at 0.02 MPa to obtain a black (K) image. Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ^{2 with} an ultrahigh pressure mercury lamp from the resin layer side, and then heat treated at 220 ° C. for 15 minutes.
The substrate on which the K image was formed was washed again with a brush as described above, and after pure water shower washing, the silane coupling solution was not used and was sent to a substrate preheating device.

-Formation of red (R) pixels-
Using the photosensitive resin transfer material R1, heat-treated red (R) pixels were obtained in the same process as the photosensitive resin transfer material K1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate-based developer was performed at 35 ° C. for 35 seconds.
Table 7 shows the thickness of the photosensitive resin layer R1 and the coating amounts of the pigments (CIPR 254 and CIPR 177).
The substrate on which the K image and the R pixel were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating apparatus.

-Formation of green (G) pixels-
Using the photosensitive resin transfer material G1, heat-treated green (G) pixels were obtained in the same process as the photosensitive resin transfer material R1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate-based developer was 34 ° C. and 45 seconds.
Table 7 shows the thickness of the photosensitive resin layer G1 and the coating amounts of the pigments (CIPG36 and CIPY150).
The substrate on which the K image and R and G pixels were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling solution was not used and the substrate was sent to a substrate preheating apparatus.

-Formation of blue (B) pixels-
Using the photosensitive resin transfer material B1, heat-treated blue (B) pixels were obtained in the same process as the photosensitive resin transfer material R1. However, the exposure amount was 30 mJ / cm ² , and development with a sodium carbonate-based developer was 36 ° C. for 40 seconds.
Table 7 shows the thickness of the photosensitive resin layer B1 and the coating amounts of the pigments (CIPB15: 6 and CIPVV23).

The substrate on which the R, G, B pixel and K images were formed was baked at 240 ° C. for 50 minutes to obtain the desired color filter.

(Example 7)
In Example 6, the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1, respectively, the colored photosensitive resin composition K2, The photosensitive resin transfer materials K2, R2, G2, and B2 were prepared in the same manner as described above except that the colored photosensitive resin composition R2, the colored photosensitive resin composition G2, and the colored photosensitive resin composition B2 were changed. The color filter was produced.

(Example 8)
In Example 6, the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1, respectively, the colored photosensitive resin composition K3, The photosensitive resin transfer materials K3, R3, G3, and B3 were prepared in the same manner as described above except that the colored photosensitive resin composition R3, the colored photosensitive resin composition G3, and the colored photosensitive resin composition B3 were changed. The color filter was produced.

Example 9
In Example 6, the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1, respectively, the colored photosensitive resin composition K4, Photosensitive resin transfer materials K4, R4, G4, and B4 were prepared in the same manner as described above except that they were changed to colored photosensitive resin composition R4, colored photosensitive resin composition G4, and colored photosensitive resin composition B4. The color filter was produced.

(Example 10)
In Example 6, the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1 are the colored photosensitive resin composition K5 and the colored, respectively. Photosensitive resin transfer materials K5, R5, G5, and B5 were produced in the same manner as described above except that the photosensitive resin composition R5, the colored photosensitive resin composition G5, and the colored photosensitive resin composition B5 were changed. Thus, a color filter was produced.

(Comparative Example 3)
In Example 6, the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1, respectively, the colored photosensitive resin composition R101, Photosensitive resin transfer materials K101, R101, G101 and B101 were produced by the same method as above except that the colored photosensitive resin composition G101 and the colored photosensitive resin composition B101 were changed, and a color filter was produced. .

(Comparative Example 4)
In Example 7, the colored photosensitive resin composition K1, the colored photosensitive resin composition R1, the colored photosensitive resin composition G1, and the colored photosensitive resin composition B1, respectively, the colored photosensitive resin composition K102, Photosensitive resin transfer materials K102, R102, G102, and B102 are the same as described above except that the colored photosensitive resin composition R102, the colored photosensitive resin composition G102, and the colored photosensitive resin composition B102 are used. A color filter was produced.

[Evaluation]
Measurement of chromaticity, occurrence of coating unevenness, occurrence of display unevenness, and comprehensive determination of color filters were performed by the same method and standard as described above.
The evaluation results are shown in Table 7.

* 1: Thickness indicates the thickness of the photosensitive resin layer formed on the photosensitive resin transfer material before exposure.

[Production and Evaluation of Liquid Crystal Display]
Resin spacers were formed on the pixels of the color filters of Examples 6 to 10 and the color filters of Comparative Examples 3 to 4 in the same manner as in Example 1 of JP-A-2003-207787.
Next, a transparent electrode layer of ITO (Indium Tin Oxide) was formed and patterned for the PVA mode.
Further, a polyimide alignment film was provided on the patterned transparent electrode layer. After applying an epoxy resin sealing material at a position corresponding to the outer frame of the black matrix provided around the pixel group of the color filter, dropping the liquid crystal for PVA mode in a vacuum and superposing it on the counter substrate, It returned to atmospheric pressure and bonded together by pressurization by atmospheric pressure to obtain a liquid crystal cell.
Next, the bonded substrate was subjected to ultraviolet treatment to cure the sealing material.
A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both sides of the liquid crystal cell so as to be crossed Nicol. Next, FR1112H (chip type LED manufactured by Stanley Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Co., Ltd.) as a green (G) LED, and DB1112H (chip manufactured by Stanley Co., Ltd.) as a blue (B) LED A side-light type backlight was constructed using a type LED) and placed on the back side of the liquid crystal cell provided with the polarizing plate to produce a liquid crystal display device having a screen size of 25 inches.
It was confirmed that the liquid crystal display device using the color filter of the example showed better display characteristics than the liquid crystal display device using the color filter of the comparative example.

The colored photosensitive resin composition and photosensitive resin transfer material of the present invention have good chromaticity, high sensitivity at the time of curing, and can form a high-definition pattern. It is suitably used for manufacturing color filters used in liquid crystal display devices such as television monitors.
The color filter of the present invention has a high-definition pixel pattern of the color filter and excellent display characteristics. Therefore, the color filter for liquid crystal display devices (LCD) such as portable terminals, portable game machines, notebook computers, TV monitors, PALC ( (Plasma address liquid crystal), plasma display, etc.
The color filter manufacturing method of the present invention is suitable for forming a high-definition color filter pattern, and can efficiently form the color filter.
Since the liquid crystal display device of the present invention uses the color filter of the present invention, it can provide high-definition images and can be used for liquid crystal display devices (LCDs) such as portable terminals, portable game machines, notebook computers, and TV monitors. ), PALC (plasma addressed liquid crystal), plasma display and the like.

Claims (11)

A colored photosensitive resin composition comprising a binder, a polymerizable compound, a photopolymerization initiator, and a colorant,
The colored photosensitive resin composition, wherein the photopolymerization initiator is a compound represented by the following general formula (1).
However, in said general formula (1), R < ¹ > represents either an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, and R < ² > is an alkyl group, an alkyloxy group, an aryloxy group, and an alkylthio group. , An arylthio group, a halogen atom, and an alkyloxycarbonyl group, Ar represents either an aromatic ring or a heteroaromatic ring, and A represents a 4-membered ring, 5-membered ring, or 6-membered ring , And any one of 7-membered rings, and m represents an integer of 0 or more. R ¹ and A may be further substituted with a substituent. When m represents an integer of 2 or more, the R ² may be the same as or different from each other.   The colorant is pigment C.I. I. P. R. 254, and pigment C.I. I. P. R. The colored photosensitive resin composition according to claim 1, which is any one of 177.   The colorant is pigment C.I. I. P. G. 36, pigment C.I. I. P. Y. 150, and pigment C.I. I. P. Y. The colored photosensitive resin composition according to claim 1, which is any one of 138.   The colorant is pigment C.I. I. P. B. 15: 6, and pigment C.I. I. P. V. The colored photosensitive resin composition according to claim 1, which is any one of 23.   The colorable resin composition according to claim 1, wherein the colorant is a black pigment. The colored photosensitive resin composition according to any one of claims 1 to 5, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).
In the general formula (2), R ¹ represents any of an acyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group, and R ² represents an alkyl group, an alkyloxy group, an aryloxy group, and an alkylthio group. , An arylthio group, a halogen atom, and an alkyloxycarbonyl group, Ar represents an aromatic ring or a heteroaromatic ring, and A ¹ represents any of a 5-membered ring and a 6-membered ring. X ¹ represents either an oxygen atom or a sulfur atom, and m represents an integer of 0 or more. R ¹ and A ¹ may be further substituted with a substituent. When m represents an integer of 2 or more, the R ² may be the same as or different from each other. The colored photosensitive resin composition according to claim 6, wherein the compound represented by the general formula (2) is a compound represented by any one of the following general formulas (3) and (4).
However, in said general formula (3) and (4), R < ⁶ > and R < ⁸ > represents either an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, and an alkyloxycarbonyl group. R ⁷ and R ⁹ represent either an alkyl group or an alkyloxy group, X ² and X ³ represent either an oxygen atom or a sulfur atom, and A ² and A ³ represent a 5-membered ring And 6 or a 6-membered ring, and p and q each represent an integer of 0 to 6.   A photosensitive resin transfer material comprising a temporary support and a photosensitive resin layer, wherein the photosensitive resin layer comprises the colored photosensitive resin composition according to any one of claims 1 to 7. Photosensitive resin transfer material.   A color filter comprising a substrate and a photosensitive resin layer, wherein the photosensitive resin layer is the colored photosensitive resin composition according to any one of claims 1 to 7, or the photosensitive resin according to claim 8. A color filter formed using a transfer material.   A photosensitive resin layer forming step of forming a photosensitive resin layer using the colored photosensitive resin composition according to any one of claims 1 to 7 or the photosensitive resin transfer material according to claim 8, and the photosensitive resin A color filter comprising: an exposure step of exposing the photosensitive resin layer; a development step of developing the photosensitive resin layer exposed in the exposure step; and a curing step of curing the photosensitive resin layer developed in the development step Production method.   A liquid crystal display device using the color filter according to claim 9.