KR101312492B1 - Photo-curable composition and color filter using the same - Google Patents

Abstract

Provided are a color filter excellent in developability, color reproducibility and contrast, and a photocurable colored resin composition for producing the color filter.

In the photocurable composition containing a coloring agent, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, the said alkali-soluble resin is an acryl-type copolymer which uses a phosphoric acid group containing monomer and an alkylene oxide chain containing monomer as a copolymerization monomer component, and the said coloring agent Is a pigment for green (G), and the content rate of the said coloring agent in the non volatile matter of a photocurable composition is 38 mass% or more, CIE obtained from the photolithographic method using the photocurable composition and the said photocurable composition The color filter whose y value of green (G) in a chromaticity diagram is 0.59 or more.

Description

PHOTOCURABLE COMPOSITION AND COLOR FILTER USING THE SAME {PHOTO-CURABLE COMPOSITION AND COLOR FILTER USING THE SAME}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable colored resin composition and color filter suitable for producing color filters for use in liquid crystal display devices and solid state image pickup devices. The present invention relates to a photocurable colored resin composition and color filter suitable for producing a color filter having good acidity and high color reproducibility or high contrast.

The color filter is an essential component of the liquid crystal panel. The liquid crystal panel is more compact than the CRT as a display device, and is equivalent to or more than the CRT in performance.

There is a demand to reduce the cost by thinning the color filter and eliminating the need for a planarization film formed thereon. On the other hand, further improvement in color reproducibility and contrast is required. It is effective to increase the colorant concentration in the color filter in order to satisfy both requirements.

Increasing the colorant concentration inevitably leads to a decrease in the content of monomers, alkali-soluble resins, and the like, resulting in a decrease in alkali developability.

In order to improve color reproducibility and contrast, higher levels of dispersibility of colorant pigments have been required.

An active energy ray-curable resin composition containing a block copolymer having a hydrophilic segment and an hydrophobic segment having an acid group, excellent alkali solubility, good sensitivity, and excellent chemical resistance after development is disclosed (for example, a patent). See Document 1.).

As the hydrophilic segment, one formed of a phosphate group-containing monomer is exemplified, and as the hydrophobic segment, polyethylene glycol mono (meth) acrylate and polyoxyethylene mono (meth) acrylate are exemplified. Although the use to a color filter is suggested as a use of this composition, there is no description of the specific example of the composition which contained the coloring agent, and the description regarding a color characteristic is also not suggested.

Moreover, the radiation sensitive composition which used the specific copolymer for the weight average molecular weight which has a specific acidic group containing a polymeric double bond group and a phosphoric acid group is disclosed (for example, refer patent document 2).

Although it is described that a good color filter can be produced in terms of dispersion stability of the pigment, adhesion of pixels, and background contamination after development, there is no description of copolymerization with an alkylene oxide chain. In Example, 27 mass%, 18 mass%, and 27 mass% of colorant content are disclosed as R, G, and B. As shown in FIG.

Moreover, pigment dispersion stability using the resin which copolymerized the monomer of the specific structure which has resin, a monomer, a coloring agent, and whose resin component has an ethylene oxide chain or a propylene oxide chain, and a phosphoric acid group containing (meth) acrylic acid ester, and favorable fluidity | liquidity photosensitive property A coloring composition is disclosed (for example, refer patent document 3).

Moreover, as a preferable weight ratio of each component, resin: monomer: coloring agent is prescribed | regulated widely as 1-50: 1-10: 1-15.

Moreover, the photocurable composition containing urethane (meth) acrylate, monofunctional (meth) acrylate, a photoinitiator, and a polyoxyalkylene alkyl ether phosphoric acid ester is disclosed, and the optical member, such as a lens sheet, is manufactured using it. (See Patent Document 4, for example.).

(Patent Document 1) Japanese Unexamined Patent Publication No. 8-339084

(Patent Document 2) Japanese Patent Application Laid-Open No. 9-146272

(Patent Document 3) Japanese Patent Application Laid-Open No. 2004-101728

(Patent Document 4) Japanese Patent Application Laid-Open No. 2001-200022

An object of the present invention is to provide a photocurable colored resin composition having excellent dispersibility of a colorant capable of obtaining a color filter excellent in developability, color reproducibility and contrast.

Moreover, the objective of this invention is providing the color filter excellent in developability, color reproducibility, and contrast.

In view of the above circumstances, the present inventors have made intensive studies and found that the above problems can be solved by using a photocurable composition using a specific acrylic copolymer having a phosphate group and a branched EO chain as a copolymer component as an alkali-soluble resin. This invention was completed.

That is, this invention is achieved by the following means.

[일반식(1)에 있어서, R³은 수소원자 또는 메틸기를 나타낸다. (EO)_n은 폴리옥시에틸렌쇄를 나타내고, (PO)_m은 폴리옥시프로필렌쇄를 나타내고, (BO)_l은 폴리옥시부틸렌쇄를 나타낸다. n은 2∼20의 정수를 나타내고, m 및 l은 각각 0∼10의 정수를 나타낸다. 단, 2≤(m+n+l)≤30이다. R⁴는 수소원자, 탄소수 1∼12의 직쇄 또는 분기의 알킬기를 나타낸다. (EO)_n과 (PO)_m과 (BO)_l은 임의의 순서로 결합하고 있어도 좋다.]In the photocurable composition containing a <1> coloring agent, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, the said alkali-soluble resin is an acryl-type copolymer which uses a phosphate group containing monomer and an alkylene oxide chain containing monomer as a copolymerization monomer component, Moreover, the said coloring agent is a pigment for green (G), and the content rate of the said coloring agent in the non volatile matter of the said photocurable composition is 38 mass% or more, The said alkylene oxide chain containing monomer is represented by following General formula (1) The photocurable composition, wherein the polyalkylene oxide chain-containing (meth) acrylate monomer.

[In General formula (1), R <^3> represents a hydrogen atom or a methyl group. (EO) _n represents a polyoxyethylene chain, (PO) _m represents a polyoxypropylene chain, and (BO) ₁ represents a polyoxybutylene chain. n represents the integer of 2-20, m and l represent the integer of 0-10, respectively. However, 2≤ (m + n + l) ≤30. R <^4> represents a hydrogen atom, a C1-C12 linear or branched alkyl group. (EO) _n , (PO) _m and (BO) _l may be combined in any order.]

[일반식(1)에 있어서, R³은 수소원자 또는 메틸기를 나타낸다. (EO)_n은 폴리옥시에틸렌쇄를 나타내고, (PO)_m은 폴리옥시프로필렌쇄를 나타내고, (BO)_l은 폴리옥시부틸렌쇄를 나타낸다. n은 2∼20의 정수를 나타내고, m 및 l은 각각 0∼10의 정수를 나타낸다. 단, 2≤(m+n+l)≤30이다. R⁴는 수소원자, 탄소수 1∼12의 직쇄 또는 분기의 알킬기를 나타낸다. (EO)_n과 (PO)_m과 (BO)_l은 임의의 순서로 결합하고 있어도 좋다.] In the photocurable composition containing a <2> coloring agent, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, the said alkali-soluble resin is an acryl-type copolymer which uses a phosphate group containing monomer and an alkylene oxide chain containing monomer as a copolymerization monomer component, Moreover, the said coloring agent is a pigment for red (R), and the content rate of the said coloring agent in the non volatile matter of the said photocurable composition is 35 mass% or more, The said alkylene oxide chain containing monomer is represented by following General formula (1). The photocurable composition, wherein the polyalkylene oxide chain-containing (meth) acrylate monomer.

[In General formula (1), R <^3> represents a hydrogen atom or a methyl group. (EO) _n represents a polyoxyethylene chain, (PO) _m represents a polyoxypropylene chain, and (BO) ₁ represents a polyoxybutylene chain. n represents the integer of 2-20, m and l represent the integer of 0-10, respectively. However, 2≤ (m + n + l) ≤30. R <^4> represents a hydrogen atom, a C1-C12 linear or branched alkyl group. (EO) _n , (PO) _m and (BO) _l may be combined in any order.]

[일반식(1)에 있어서, R³은 수소원자 또는 메틸기를 나타낸다. (EO)_n은 폴리옥시에틸렌쇄를 나타내고, (PO)_m은 폴리옥시프로필렌쇄를 나타내고, (BO)_l은 폴리옥시부틸렌쇄를 나타낸다. n은 2∼20의 정수를 나타내고, m 및 l은 각각 0∼10의 정수를 나타낸다. 단, 2≤(m+n+l)≤30이다. R⁴는 수소원자, 탄소수 1∼12의 직쇄 또는 분기의 알킬기를 나타낸다. (EO)_n과 (PO)_m과 (BO)_l은 임의의 순서로 결합하고 있어도 좋다.]<3> A photocurable composition containing a coloring agent, an alkali soluble resin, a photopolymerizable compound and a photopolymerization initiator, wherein the alkali soluble resin is an acrylic copolymer comprising a phosphate group-containing monomer and an alkylene oxide chain-containing monomer as a copolymerization monomer component, Moreover, the said coloring agent is a pigment for blue (B), and the content rate of the said coloring agent in the non volatile matter of the said photocurable composition is 17 mass% or more, The said alkylene oxide chain containing monomer is represented by following General formula (1) The photocurable composition, wherein the polyalkylene oxide chain-containing (meth) acrylate monomer.

[In General formula (1), R <^3> represents a hydrogen atom or a methyl group. (EO) _n represents a polyoxyethylene chain, (PO) _m represents a polyoxypropylene chain, and (BO) ₁ represents a polyoxybutylene chain. n represents the integer of 2-20, m and l represent the integer of 0-10, respectively. However, 2≤ (m + n + l) ≤30. R <^4> represents a hydrogen atom, a C1-C12 linear or branched alkyl group. (EO) _n , (PO) _m and (BO) _l may be combined in any order.]

<4> The color filter whose y value of the green (G) in the CIE chromaticity diagram obtained by the photolithographic method using the photocurable composition as described in said <1> is 0.59 or more.

<5> The color filter whose x value of red (R) in the CIE chromaticity diagram obtained by the photolithographic method using the photocurable composition as described in said <2> is 0.60 or more.

<6> Color filter whose y value of blue (B) in the CIE chromaticity diagram obtained by the photolithographic method using the photocurable composition as described in said <3> is 0.10 or less.

`` Photocurable composition ''

The 1st aspect of the photocurable composition (henceforth a "composition of this invention" of this invention) of this invention is a photocurable composition containing a coloring agent, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, The said alkali-soluble resin is It is an acryl-type copolymer which uses a phosphoric acid group containing monomer and an alkylene oxide chain containing monomer as a copolymerization monomer component, The said coloring agent is a pigment for green (G), and the content rate of the said coloring agent in the non volatile matter of the said photocurable composition is 38 It is characterized by being more than mass%.

A second aspect of the photocurable composition of the present invention is a photocurable composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, wherein the alkali-soluble resin is a copolymerizable monomer comprising a phosphate group-containing monomer and an alkylene oxide chain-containing monomer. It is an acryl-type copolymer used as a component, The said coloring agent is a pigment for red (R), The content rate of the said coloring agent in the non volatile matter of the said photocurable composition is 35 mass% or more, It is characterized by the above-mentioned.

A third aspect of the photocurable composition of the present invention is a photocurable composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound and a photopolymerization initiator, wherein the alkali-soluble resin is a copolymerizable monomer comprising a phosphate group-containing monomer and an alkylene oxide chain-containing monomer. It is an acryl-type copolymer used as a component, The said coloring agent is a pigment for blue (B), and the content rate of the said coloring agent in the non volatile matter of the said photocurable composition is 17 mass% or more, It is characterized by the above-mentioned.

The composition of this invention contains a solvent, a pigment derivative, surfactant, dispersing agents, such as a polar group containing polymer, etc. as needed.

By containing a dispersing agent, stability of the photocurable composition of this invention can improve and storage stability over a long term can be improved.

Hereinafter, each component contained in the composition (photocurable composition of a 1st-3rd aspect) of this invention is demonstrated in detail.

<Alkali-soluble resin>

Alkali-soluble resin used for the composition of this invention is an acryl-type copolymer which makes at least a phosphoric acid group containing monomer (acid component monomer: monomer 1) and an alkylene oxide chain containing monomer as a copolymerization monomer component (henceforth "acrylic air in this invention. Also known as "union."

Moreover, the acryl-type copolymer in this invention can be synthesize | combined by copolymerizing the said monomer component normally with radical polymerization, coordination polymerization, cationic polymerization, anionic polymerization, etc.

As polystyrene conversion mass mean molecular weight (Mw) by GPC of the acryl-type copolymer in this invention, Preferably it is 3,000-100,000, More preferably, it is 5,000-30,000.

(Phosphate-containing monomer)

The phosphoric acid group-containing monomer in the present invention can be used without particular limitation as long as it has an ethylenically unsaturated group and a phosphoric acid group.

From the viewpoint of easy polymerization and availability, among these, at least one phosphate ester monomer selected from methacryloxyethyl phosphate, bis (methacryloxyethyl) phosphate and methacryloxyethylene glycol phosphate Preferably, specifically [H ₂ C = CR ¹ -CO-O- (CH ₂ ) _n -O-] _m PO (OH) _3-m , [H ₂ C = CR ² -CO-O- (C ₂ H ₅ O) _n -O-] _m PO (OH) _3-m and the like. Where m is an integer of 1 or 2, n is 1 to 20, preferably from 1 to 10, and most preferably an integer of 1~5, R ^1, R ² are each independently H or CH _3.

As content (molar ratio) as a monomer component of the said phosphate group containing monomer with respect to the acryl-type copolymer in this invention, 5-35 mol% is preferable and 10-25 mol% is more preferable. When content of the said phosphate group containing monomer does not fall within the said range, alkali solubility may fall, and when exceeding the said range, the solubility to a solvent may fall.

(Alkylene oxide chain-containing monomer)

The alkylene oxide chain-containing monomer in the present invention is not particularly limited as long as it is a polymerizable monomer having an alkylene oxide chain, but it is a polyalkylene oxide chain-containing (meth) acrylate monomer represented by the following general formula (1). Is preferably.

In General formula (1), R <^3> represents a hydrogen atom or a methyl group. In General Formula (1), (EO) _n represents a polyoxyethylene chain, (PO) _m represents a polyoxypropylene chain, and (BO) ₁ represents a polyoxybutylene chain.

In General formula (1), the bonding order of (EO) _n , (PO) _m, and (BO) ₁ can be arbitrarily determined. The polyoxyethylene chain (EO) _n is an adduct of ethylene oxide, and the number of additions of ethylene oxide is represented by n.

The polyoxypropylene chain (PO) _m is an adduct of propylene oxide, and the number of additions of propylene oxide is represented by m. The polyoxybutylene chain (BO) _l is an adduct of butylene oxide, and the number of additions of butylene oxide is represented by l.

In General formula (1), n represents the integer of 2-20, m and l represent the integer of 0-10, respectively. As said n, the integer of 4-15 is preferable, As said m, the integer of 0-10 is preferable, As said l, the integer of 0-10 is preferable. However, it is preferable that it is 2 <= (m + n + l) <= 30, and 4 <= (m + n + l) <= 20.

R <^4> in General formula (1) represents a hydrogen atom, a C1-C12 linear or branched alkyl group, or group represented by following General formula (2), and a linear or branched alkyl group is preferable. As said linear or branched alkyl group, a C1-C4 alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group are mentioned specifically ,.

In general formula (2), R <^5> represents a hydrogen atom or a C1-C13 linear or branched alkyl group, and a hydrogen atom or a C1-C3 alkyl group is preferable. As said alkyl group, a C1-C3 alkyl group is preferable, and methyl, ethyl, and isopropyl are specifically, preferable. Moreover, p represents the integer of 0-5, and the integer of 0-2 is preferable.

As content (molar ratio) as a monomer component of the polyoxyalkylene chain containing (meth) acrylate monomer represented by the said General formula (1) with respect to the acryl-type copolymer in this invention, 2-20 mol% is preferable, and 3- 10 mol% is more preferable. Moreover, if content of the polyoxyalkylene chain containing (meth) acrylate monomer represented by the said General formula (1) does not fall within the said range, the applicability | paintability to the board | substrate of the coating liquid containing a photocurable colored resin composition will not become enough. It may become impossible to achieve this invention effectively. Moreover, when it exceeds the said range, the dispersibility or solubility of a coloring agent may fall.

As a polyoxyalkylene chain containing (meth) acrylate monomer represented by the said General formula (1), for example, ethylene oxide modified cresol acrylate (m = 4, brand name: Aronix TO-901), ethylene oxide modified dodecyl acryl Rate (m = 10, brand name: Aaronics TO-950), ethylene oxide modified tridecyl acrylate (m = 10, brand name: Aaronics TO-951), 2-ethylhexyl polyethylene glycol acrylate (m = 4, brand name) : Aaronics TO-946), 2-ethylhexyl polyethylene glycol acrylate (m = 8, brand name: Aaronics TO-947), 2-ethylhexyl polyethylene glycol acrylate (m = 12, brand name: Aaronics TO-948 ), 2-ethylhexyl polyethylene glycol acrylate (m = 20, brand name: Aronix TO-949), the above Toagosei Co., Ltd. product;

Ethoxy-diethylene glycol acrylate (m = 2, brand name: light acrylate EC-A), methoxy- triethylene glycol acrylate (m = 3, brand name: light acrylate MTG-A), methoxy-polyethylene Glycol acrylate (m = 9, brand name: light acrylate 130A), phenoxy-polyethylene glycol acrylate (m = 2, brand name: light acrylate P-200A), nonylphenyl-polyoxyethylene chain adduct acrylate ( m = 4, brand name: light acrylate NP-4EA), nonylphenyl- polyoxyethylene chain adduct acrylate (m = 8, brand name: light acrylate NP-8EA), the above Kyoeisha Chemical Co., Ltd. product;

Polyethylene glycol acrylate (m'6-8, brand name: Brenmer AE-350), polyethylene glycol methacrylate (m'2, brand name: Brenmer PE-90), polyethylene glycol methacrylate (m'4-5) , Brand name: Brenmer PE-200, polyethylene glycol methacrylate (m'7-9, brand name: Brenmer PE-350), methoxy polyethylene glycol monoacrylate (m'2, brand name: Brenmer AME-400 ), Methoxy polyethylene glycol methacrylate (m'2, trade name: Brenmer PME-100), methoxy polyethylene glycol methacrylate (m'4, trade name: Brenmer PME-200), methoxy polyethylene glycol methacrylate Rate (m'9, brand name: Brenmer PME-400), polypropylene glycol methacrylate (n'9, brand name: Brenmer PP-500), polypropylene glycol methacrylate (n'12, brand name: Brenmer PP-800), polyethylene glycol polypropylene glycol methacrylate (m = 7, n = 3, brand name: blender 70PEP-370B), polyethylene Recall polytetramethylene glycol methacrylate (m = 10, n = 5, brand name: Brenmer 50PET-800), octoxy polyethylene glycol polypropylene glycol monomethacrylate (m'8, n'6, brand name: Brenmer 50POEP-800B), octoxy polyethylene glycol polyoxypropylene glycol monomethacrylate (m # 8, n # 6, brand name: Brenmer 50AOEP-800B), and the Nihon Yushi Corporation make;

Methoxydiethylene glycol methacrylate (m = 2, brand name: NK ester M-20G), methoxydiethylene glycol methacrylate (m = 4, brand name: NK ester M-40G), methoxydiethylene glycol methacrylate ( m = 9, brand name: NK ester M-90G), phenoxy diethylene glycol acrylate (m = 2, brand name: NK ester AMP-20G), the above Shin-Nakamura Kagaku Kogyo Co., Ltd. product, etc. are mentioned.

(Other monomer component)

Monomer 3-

The acryl-based copolymer in the present invention, together with the monomers 1 and 2, as one of the monomer components, benzyl methacrylate (BzMA), styrene (St), methyl styrene, benzyl acrylate and the like (hereinafter referred to as "monomer 4") It may be referred to.). Among these, benzyl methacrylate is preferable. The strength of the coating film obtained by the composition of this invention can be improved by using benzyl methacrylate further as a monomer component of the acryl-type copolymer in this invention. As said benzyl methacrylate, what is represented by following General formula (3) can be used preferably.

In General formula (3), R <^6> represents a hydrogen atom or a methyl group. R <^7> represents a hydrogen atom and a C1-C6 alkyl group, and a hydrogen atom, a methyl group, and an ethyl group are preferable. In General Formula (4), q represents an integer of 0 to 5, and 0 to 2 are preferable.

As content (molar ratio) as a monomer component of the said benzyl methacrylate with respect to the acryl-type copolymer in this invention, it is preferable that it is 50 mol% or less, More specifically, 0-40 mol% is more preferable. When content of benzyl methacrylate exceeds 50 mol%, thixotropy of a solution may become large and the film thickness uniformity of a coating film may fall easily.

Monomer 4-

In addition, the acryl-type copolymer in this invention is hydroxyethyl (meth) acrylate (HEMA, HEA), hydroxypropyl (meth) acrylate, and 2-hydroxy as one of the monomer components with the said monomers 1-2. It can contain at least 1 sort (it may be called "monomer 4" hereafter) chosen from 3-phenoxypropyl (meth) acrylate. By further using monomer 4 as the monomer component of the acrylic copolymer in the present invention, it is possible to improve the heat resistance of the coating film obtained by the composition of the present invention and to form a coating film having high adhesion to a substrate or the like. Peeling of a coating film can be prevented.

As said monomer 4, hydroxyethyl (meth) acrylate is especially preferable. As said monomer 4, for example, hydroxypropyl methacrylate (brand name: Brenmer P, the Nippon Yushi Co., Ltd. product), 2-hydroxy-3- phenoxypropyl (meth) acrylate (brand name: Aronix M- 5700, the Tokagaku Co., Ltd. product, 2-hydroxypropyl acrylate (brand name: light ester HOP-A, the Kyoeisha Chemical Co., Ltd. product) are mentioned.

The content (molar ratio) of the monomer 4 of the monomer 4 to the acrylic copolymer in the present invention is preferably 30 mol% or less, more preferably 20 mol% or less, and more preferably 3 to 10 mol%. Do. When content of the said monomer 5 exceeds 30 mol%, thixotropy as a coating liquid becomes large and the coating film uniformity of a coating film may fall easily.

(Other alkali soluble resin)

In the composition of this invention, alkali-soluble resin of another structure can be used together as said alkali-soluble resin other than the acryl-type copolymer in this invention. For example, the copolymer which consists of (meth) acrylic acid and benzyl methacrylate, or the copolymer which consists of (meth) acrylic acid, benzyl methacrylate, and hydroxyethyl (meth) acrylate, etc. are preferable.

When the acrylic copolymer in this invention is used independently as said alkali-soluble resin, the content rate of alkali-soluble resin in the composition of this invention has preferable 10-50 mass% with respect to total solid, 10-40 mass % Is more preferable.

Moreover, when using alkali-soluble resin of another structure together, 10-50 mass% is preferable for the total content rate of the other alkali-soluble resin in the composition of this invention. In the composition of this invention, when there is too little content of alkali-soluble resin, alkali image development may not advance. On the other hand, when too much, the viscosity as a coating liquid will become high, coating thickness uniformity may deteriorate, application | coating spots may arise easily, and developing latitude may also fall.

<Colorant>

As a coloring agent in the 1st aspect of the composition of this invention, it is necessary to contain the pigment for green (G), and to make the content rate of the said coloring agent in the non volatile matter of a photocurable composition into 38 mass% or more.

As said green (G) pigment, you may use individually by 1 type, or may use multiple together.

As a coloring agent in the 2nd aspect of the composition of this invention, it is necessary to contain the pigment for red (R), and to make content rate of the said coloring agent in the non volatile matter of a photocurable composition into 35 mass% or more.

As said red (R) pigment, you may use individually by 1 type, or may use multiple together.

As a coloring agent in the 3rd aspect of the composition of this invention, it is necessary to contain the pigment for blue (B), and to make content rate of the said coloring agent in the non volatile matter of a photocurable composition into 17 mass% or more.

As said blue (B) pigment, you may use individually by 1 type, or may use multiple together.

As a pigment which can be used for the composition of this invention, various conventionally well-known inorganic pigments or organic pigments can be used. In addition, considering that it is preferable to have a high transmittance, whether inorganic pigments or organic pigments, the use of fine ones is preferable, and considering handling properties, the average particle diameter of the pigment is preferably 0.01 μm to 0.1 μm, and 0.01 μm to 0.05 micrometers is more preferable.

Examples of the inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like, and specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony; The complex oxide of the said metal is mentioned.

As said organic pigment, for example,

C.I.Pigment Yellow

11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;

C.I. Pigment Orange 36,38,43,71;

C.I.Pigment Red

81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;

C.I. Pigment Violet 19,23,32,39;

C.I. Pigment Blue 1,2,15,15: 1,15: 3,15: 6,16,22,60,66;

C.I. Pigment Green 7,36,37;

C.I. Pigment Brown 25,28;

C.I. Pigment Black 1,7;

Carbon black etc. are mentioned.

Especially in this invention, what has basic N atom in the structural formula of a pigment can be used preferably. Pigments having these basic N atoms exhibit good dispersibility in the compositions of the present invention. Although the cause is not fully elucidated, it is presumed that the affinity of a photopolymerizable compound and a pigment has influenced.

The following are mentioned as a pigment used preferably in this invention. However, the present invention is not limited thereto.

C.I.Pigment Yellow

11,24,108,109,110,138,139,150,151,154,167,180,185,

C.I. Pigment Orange 36,71,

C.I.Pigment Red 122,150,171,175,177,209,224,242,254,255,264,

C.I. Pigment Violet 19,23,32,

C.I.Pigment Blue 15: 1,15: 3,15: 6,16,22,60,66,

C.I.Pigment Black 1

As a coloring agent of the composition of the 1st aspect of this invention, it is a pigment for green (G) as mentioned above.

As the pigment for green (G), a halogenated phthalocyanine pigment alone or a mixture of this and a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin yellow pigment is used. It is preferable.

For example, CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment Yellow 185 Is preferred.

The mass ratio of green pigment and yellow pigment is preferably 100: 5 to 100: 150. When the said mass ratio is less than 100: 5, it may become difficult to suppress the light transmittance of 400 nm-450 nm, and color purity may not be raised. If it exceeds 100: 150, the dominant wavelength becomes near the long wavelength, and the deviation from the NTSC target color may increase. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

Although the content rate of the coloring agent (pig for G) in the composition of 1st aspect of this invention is 38 mass% or more in the non volatile matter of a composition, 38-70 mass% is preferable from a viewpoint of a color characteristic, and 40-60 mass % Is particularly preferred.

When there are too few coloring agents, there exists a tendency for suitable chromaticity to be unable to be obtained as a color filter. On the other hand, when too much, photocuring does not fully advance, the intensity | strength as a film | membrane falls, and the development latitude at the time of alkali image development tends to become narrow.

As a coloring agent of the composition of the 2nd aspect of this invention, it is necessary to contain the pigment for red (R) as mentioned above.

Examples of the pigment for red (R) include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of these, disazo yellow pigments, isoindolin yellow pigments, and quinophthalone yellows. It is preferable to use a mixture of pigments or perylene-based pigments.

For example, CI pigment red 177 is mentioned as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 can be mentioned as a perylene pigment, CI pigment red 254 is a diketopyrrolopyrrole pigment. Can be mentioned.

You may mix with C.I. pigment yellow 139 from the point of color reproducibility. In addition, the mass ratio of the red pigment and the yellow pigment is preferably 100: 5 to 100: 50. Below 100: 4, it is difficult to suppress the light transmittance from 400 nm to 500 nm, and color purity may not be improved. At 100: 51 or more, the dominant wavelength is near the short wavelength, and the deviation from the NTSC target color may increase. Especially as said mass ratio, the range of 100: 10-100: 30 is optimal. Moreover, in the case of the combination of red pigments, it can adjust to chromaticity.

Although the content rate of the coloring agent (pig for R) in the composition of the 2nd aspect of this invention needs to be 35 mass% or more in the non volatile matter of a composition, 35-75 mass% is preferable from a viewpoint of a color characteristic, 37 70 mass% is more preferable, and its 39-65 mass% is especially preferable.

When there are too few coloring agents, there exists a tendency for suitable chromaticity to be unable to be obtained as a color filter. On the other hand, when too much, photocuring does not fully advance, the intensity | strength as a film | membrane falls, and the development latitude at the time of alkali image development tends to become narrow.

As a coloring agent of the composition of the 3rd aspect of this invention, it is a pigment for blue (B) as mentioned above.

As said blue (B) pigment, a phthalocyanine type pigment can be used individually, or the mixture of this and a dioxadine type purple pigment can be used. For example, a mixture of C.I. Pigment Blue 15: 6 and C.I.Pigment Violet 23 is preferable. As for mass ratio of a blue pigment and a purple pigment, 100: 0-100: 30 are preferable, More preferably, it is 100: 10 or less.

Although the content rate of the coloring agent (pig for B) in the composition of the 3rd aspect of this invention needs to be 17 mass% or more in the non volatile matter of a composition, 17-70 mass% is preferable from a viewpoint of a color characteristic, 19 65 mass% is more preferable, and 21-60 mass% is especially preferable.

When there are too few coloring agents, there exists a tendency for suitable chromaticity to be unable to be obtained as a color filter. On the other hand, when too much, photocuring does not fully advance, the intensity | strength as a film | membrane falls, and the development latitude at the time of alkali image development tends to become narrow.

In the composition of the present invention, dyes can be used as colorants within a range that does not impair the effects of the present invention.

There is no restriction | limiting in particular as dye which can be added to the composition of this invention, The well-known dye for conventional color filters can be used. For example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, Japanese Patent Registration 2592207, US Patent No. 4,808,501, US Patent No. 5,667,920, US Patent No. 5,059,500, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115, Japanese Patent Laid-Open No. 6-194828, Japanese Patent Laid-Open No. 8-211599, Japanese Patent Laid-Open No. 4-249549, Japanese Patent Laid-Open No. 10-123316, Japanese Patent Laid-Open No. 11-302283, Japanese Patent Laid-Open No. 7-286107, Japanese Patent Laid-Open No. 2001-4823, Japanese Patent Laid-Open No. 8-15522, Japanese Patent Laid-Open No. 8-29771, Japanese Patent Laid-Open No. 8-146215, Japan Japanese Patent Laid-Open No. 11-343437, Japanese Patent Laid-Open No. 8-62416, Japan Patent Publication 2002-14220, Japanese Patent Publication 2002-14221, Japanese Patent Publication 2002-14222, Japanese Patent Publication 2002-14223, Japanese Patent Publication No. 8-302224, Japanese Patent Publication The pigment | dye disclosed by Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531, etc. can be used.

Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, phenothiazine and pi Dye, such as a rolopyrazole azomethine series, a xanthene series, a phthalocyanine series, a benzopyran series, an indigo series, can be used.

In the case of a resist system which develops water or alkali, acid dyes and / or derivatives thereof may be used in a range that does not impair the effects of the present invention from the viewpoint of completely removing the binder and / or dye of the unilluminated portion by development. There may be cases.

In addition, direct dyes, basic dyes, mordant dyes, acidic mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes and / or derivatives thereof may also be used.

The acid dye is not particularly limited as long as it has an acid group such as sulfonic acid or carboxylic acid, but is not particularly limited, solubility in an organic solvent or developer, salt formation with a basic compound, absorbance, interaction with other components in the composition, light resistance, The heat resistance is selected in consideration of all the required performance.

Although the specific example of the said acid dye is given to the following, it is not limited to these. For example,

acid alizarin violet N; acid black 1,2,24,48; acid blue 1,7,9,15,18,23,25,27,29,40,45,62,70,74,80,83,86,87,90,92,103,112,113,120,129,138,147,158,171,182,192,243,324: 1; acid chrome violet K; acid Fuchsin; acid green 1,3,5,9,16,25,27,50; acid orange 6,7,8,10,12,50,51,52,56,63,74,95; acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91,92,94,97,103,111,114,129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274; acid violet 6B, 7, 9, 17, 19; acid yellow 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184,243; Food Yellow 3; And derivatives of these dyes.

Among these, the acid dyes include acid black 24; acid blue 23,25,29,62,80,86,87,92,138,158,182,243,324: 1; acid orange 8,51,56,63,74; acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; acid violet 7; acid yellow 17,25,29,34,42,72,76,99,111,112,114,116,184,243; Dyes such as acid green 25 and derivatives of these dyes are preferred.

Azo-based, xanthene-based, and phthalocyanine-based acid dyes other than those described above are also preferable, and C. I. Solvent Blue 44,38; C.I. Solvent orange 45; Acid dyes such as Rhodamine B and Rhodamine 110 and derivatives of these dyes are also preferably used.

Although the coloring agent content rate in the total solid of the composition (1st-3rd aspect) of this invention is not specifically limited, Preferably it is 30-60 mass%. When there are too few coloring agents, it exists in the tendency for a suitable chromaticity to not be acquired as a color filter. On the other hand, when too much, photocuring does not fully advance, the intensity | strength as a film | membrane falls, and the development latitude at the time of alkali image development tends to become narrow.

In the present invention, a conventionally known pigment dispersant and a surfactant can be added for the purpose of improving the dispersibility of the pigment. Although many kinds of compounds are used as these dispersing agents, For example, Disperbyk161 (30 mass% solution of the mixed solvent of propylene methylglycol acetate of a block copolymer and butyl acetate) (Bikkemi Co., Ltd. product), a phthalocyanine derivative (commercially available EFKA- 745 (manufactured by Efca Co.)), Solsper's 5000 (manufactured by Geneca Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsukagaku Kogyo Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75, Cationic surfactants such as No. 90, No. 95 (manufactured by Kyoesha Yushi Kagaku Kogyo Co., Ltd.) and W001 (manufactured by Yutakasho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxy Nonionic surfactants such as ethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; Anionic surfactants such as W005 and W017 (manufactured by Yutaka Sho); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (above Morishita Sangyo Co., Ltd.) Polymer dispersing agents such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15 and Disperse Aid 9100 (manufactured by Sanofuco); Various solvent dispersants (manufactured by Geneca Co., Ltd.), such as 28000 and 28000; Adecatronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108 , L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (Bikkemi Co., Ltd. product) is mentioned.

<Photopolymerizable compound>

Next, the photopolymerizable compound used in the composition of the present invention will be described.

As said photopolymerizable compound, the compound which has at least 1 addition-polymerizable ethylene group, and has an ethylenically unsaturated group which has a boiling point of 100 degreeC or more under normal pressure is preferable, Especially, a tetrafunctional or more acrylate compound is more preferable.

As a compound which has said at least 1 addition-polymerizable ethylenically unsaturated group, and whose boiling point is 100 degreeC or more at normal pressure, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc. Monofunctional acrylate and methacrylate; Polyethylene glycol di (meth) acrylate, trimethol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimetholethane, etc. (Meth) acrylated after addition of ethylene oxide or propylene oxide to polyfunctional alcohols; poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Japan Urethane acrylates described in Patent Publication Nos. 50-6034, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 48-64183, Polyfunctional acrylates, such as the polyester acrylates described in this patent publication 49-43191 and Japanese patent publication 52-30490, and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid And methacrylate. Also, 20, No. 7, and pages 300 to 308 which are introduced as photocurable monomers and oligomers can also be used.

Furthermore, a compound obtained by adding ethylene oxide or propylene oxide to the above-mentioned polyfunctional alcohol and then (meth) acrylated is described in Japanese Patent Application Laid-open No. Hei 10-62986 as general formulas (1) and (2) together with the specific examples thereof. These can also be used as a photopolymerizable compound.

Especially, the structure where dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups via ethylene glycol and a propylene glycol residue are preferable. These oligomer types are also used. These photopolymerizable compounds can be used individually by 1 type or in combination of 2 or more types.

The usage-amount of these photopolymerizable compounds is 20-200 mass%, More preferably, it is 50-120 mass% with respect to the total solid 100 of a photocurable colored resin composition. Even if the amount of the photopolymerizable compound to be used is at least and too large in excess of the above range, curing becomes insufficient, which is not preferable.

<Photopolymerization initiator>

As said photoinitiator, For example, halomethyloxadiazole of Unexamined-Japanese-Patent No. 57-6096; Active halogen compounds such as halomethyl-s-triazine described in JP-A-59-1281, JP-A-53-133428, and the like; Aromatic carbonyl compounds such as ketal, acetal or benzoin alkyl ethers described in US Patent USP-4318791, European Patent Publication EP-88050A and the like; Aromatic ketone compounds such as benzophenones described in US Patent USP-4199420; (Thio) xanthones or acridines compounds described in Fr-2456741; Compounds such as coumarins or ropindimers described in JP-A-10-62986; Sulfonium organoboron complexes such as Japanese Patent Application Laid-Open No. 8-015521; Etc. may be used.

In the present invention, as the photopolymerization initiator, acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyl oxadiazole series, acridine series, coumarin series, and ropin dimer series It is preferable to use photoinitiators, such as a biimidazole type.

As said acetophenone type photoinitiator, 2, 2- diethoxy acetophenone, p-dimethylamino acetophenone, 2-hydroxy-2-methyl-1- phenyl- propane- 1-one, p-dimethylamino aceto, for example Phenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, etc. are mentioned preferably.

As said ketal type photoinitiator, benzyl dimethyl ketal, benzyl- (beta)-methoxyethyl acetal, etc. are mentioned preferably, for example.

As said benzophenone type photoinitiator, a benzophenone, 4,4'- (bisdimethylamino) benzophenone, 4,4'- (bisdiethylamino) benzophenone, 4,4'- dichloro benzophenone, 1, for example -Hydroxycyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropaneone-1 etc. are mentioned preferably.

As said benzoin type or benzoyl type photoinitiator, benzoin isopropyl ether, benzoin isopropyl ether, benzoin methyl ether, methyl o-benzoyl benzoate, etc. are mentioned preferably, for example.

As said xanthone type photoinitiator, diethyl thioxanthone, diisopropyl thioxanthone, monoisopropyl thioxanthone, chloro thioxanthone, etc. are mentioned preferably, for example.

As said triazine type photoinitiator, it is 2, 4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2, 4-bis (trichloromethyl) -6-p-methoxy, for example. Styryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis ( Trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl- 2,6-di (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxy styryl-2,6-di (Trichloromethyl) -s-triazine, 4-benoxoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonyl Amino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s -Triazine etc. are mentioned preferably.

As said halomethyloxadiazole type photoinitiator, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole and 2-trichloromethyl-5- (cyanostyryl) -1,3, for example , 4-oxodiazole, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl -1,3,4-oxodiazole etc. are mentioned preferably.

As said acridine-type photoinitiator, 9-phenyl acridine, 1, 7-bis (9-acridinyl) heptane, etc. are mentioned preferably, for example.

As said coumarin type photoinitiator, it is 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino- ((s- Triazine-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, etc. are mentioned preferably.

As said lopin dimer type photoinitiator, 2- (o-chlorophenyl) -4,5-diphenyl imidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenyl imida, for example Zolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, etc. are mentioned preferably.

As said biimidazole type photoinitiator, 2-mercapto benzimidazole, 2,2'- benzothiazolyl disulfide, etc. are mentioned preferably, for example.

In addition, as said photoinitiator, 1-phenyl- 1, 2- propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4'- (benz mercapto) benzoyl-hexyl- ketoxime, 2 And 4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylphosphonium salt, and the like.

In this invention, it is not limited to the above photoinitiator, Another well-known thing can also be used. For example, bisinal polyketolaldonyl compounds disclosed in US Pat. No. 2,367,660, α-carbonyl compounds disclosed in US Pat. Nos. 2,367,661 and 2,367,670, US Pat. No. 2,448,828. Acyloinethers, aromatic acyloin compounds substituted with α-hydrocarbons as disclosed in US Pat. No. 2,722,512, multinuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. No. 3,549,367 Combinations of triallylimidazole dimers / p-aminophenyl ketones disclosed in the specification and benzothiazole compounds / trihalomethyl-s-triazine compounds disclosed in Japanese Patent Publication No. 51-48516 Can be mentioned.

Moreover, these photoinitiators can also be used together.

The usage-amount of the said photoinitiator is 0.1-10.0 mass% of the total solid of a photocurable colored resin composition, Preferably it is 0.5-5.0 mass%. When the usage-amount of a photoinitiator is less than 0.1 mass%, superposition | polymerization may not progress easily, and when it exceeds 10.0 mass%, film strength may become weak.

<Solvent>

A solvent can be used when preparing the composition of this invention. Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl acetate, ethyl butyrate, butyl butyrate, and alkyl esters. , Methyl lactate, ethyl lactate, methyl oxy acetate, ethyl oxy acetate, butyl oxy acetate, methyl methoxy acetate, ethyl methoxy acetate, butyl butyl acetate, ethoxy acetate, ethyl ethoxy acetate, methyl 3-oxypropionate, 3-oxypropionic acid alkyl esters, such as 3-oxyethyl propionate; Methyl 3-methoxy propionate, 3-methoxy ethylpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate , 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetic acid, ethyl acetate, methyl 2-oxobutyrate, 2-oxo Ethyl butane and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene, xylene and the like.

Of these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexa Paddy fields, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used as the solvent in the present invention.

These solvents may be used alone or in combination of two or more thereof.

<Fluorinated Organic Compound>

In the composition of this invention, you may contain the fluorine-type organic compound whose fluorine content rate is 3-40 mass%. The characteristic as a coating liquid of a composition can be improved further.

The fluorine content rate of the said fluorine-type organic compound is 3-40 mass%, Preferably it is 5-30 mass%, More preferably, it is 7-25 mass%.

When the fluorine content of the fluorine-based organic compound is low, sufficient effects cannot be obtained in coating thickness uniformity and liquid saving properties. On the contrary, when the content is too large, solubility in the composition may be insufficient.

By incorporating the fluorine-based organic compound into the composition of the present invention, the liquid characteristics as the coating liquid can be improved, and the uniformity and liquid saving property of the coating thickness can be improved. In particular, the coating property to a board | substrate improves and the coating film of the uniform film thickness without thickness deviation can be obtained even with a small amount of liquid.

As said fluorine-type organic compound, Megapack F171, copper F172, copper F173, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437 (above, Dai Nippon Ink Co., Ltd. product), Florard FC430, Copper FC431, Copper FC171 (above, Sumitomo 3M Co., Ltd.), Supron S-382, Copper SC-101, Copper SC-103, Copper SC-104, Copper SC-105, Copper SC1068, And SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

In addition, by containing the fluorine-based organic compound, the fluidity as the coating liquid is improved, the interfacial tension between the substrate and the coating liquid is reduced, the wettability to the substrate is improved, and even a thin film having a thickness of several micrometers can obtain a coating film having a small thickness variation. have. Particularly, when the coating film becomes thin, good results are obtained for slit coating that is liable to cause coating stains, thickness variations, and liquid dropping from the coating surface.

As addition amount of the said fluorine-type organic compound, Preferably it is 0.001-2.0 mass% with respect to the whole coating solution, More preferably, it is 0.005-1.0 mass%.

&Lt; Other components >

If necessary, various additives, for example, fillers, polymer compounds other than the alkali-soluble resin, surfactants other than the above, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, and the like can be added to the composition of the present invention.

Specific examples of these additives include fillers such as glass and alumina; Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, addition of acid anhydride to a polymer having a hydroxyl group, formed of alcohol soluble nylon, bisphenol A and epicrohydrin Alkali-soluble resins such as phenoxy resins; Surfactants such as nonionics, cationics and anionics, specifically, phthalocyanine derivatives (commercially available EFKA-745 (Morishita); Organosiloxane Polymer KP341 (made by Shin-Etsukagaku Kogyo Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow Nos. 75, No.90, No.95 (Kyoesha Yushi Kagaku Kogyo Co., Ltd.), W001 (Yutakasho) Cationic surfactants such as products); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Esters (nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 from BASF; W004, W005, W017 (Yutaka Anionic surfactants such as SHOW), EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (more than Morishitasan), Disperse Aid 6, and Dis. Polymer dispersants, such as Perth Aid 8, Disperse Aid 15, and Disperse Aid 9100 (manufactured by Sanofuco); (Geneca Co., Ltd. product); Adecatronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (made by Asahi Denka) and Isonet S- 20 (product of Sanyokasei);

Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; And anti-agglomerating agents such as sodium polyacrylate.

In addition, in order to promote alkali solubility of the unilluminated portion and to further improve the developability of the composition of the present invention, the composition of the present invention may contain an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. Addition can be performed. Specifically, For example, aliphatic monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, gil acetic acid, pivalic acid, capronic acid, diethyl acetic acid, enanthic acid, and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, sublinic acid, azeline acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and canforonic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemimelitic acid, and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melotropic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamic acid, methyl cinnamic acid, benzyl cinnamic acid, cinnamilidene acetic acid, cumalic acid, and unbelic acid. .

In addition to the above, it is preferable to add a thermal polymerization inhibitor to the composition of the present invention, and for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogarol, t-butyl Catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercapto Benzoimidazole and the like are useful.

<Method of manufacturing and using photocurable colored resin composition of the present invention>

The composition of the present invention is prepared by subjecting a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other additives used as needed to undergo a mixing and dispersing step of mixing and dispersing the mixture using various mixers and dispersers. can do.

In addition, the mixing and dispersing step preferably comprises a kneading dispersion and a non-dispersion treatment performed subsequently. However, the kneading dispersion can be omitted.

As a preferable manufacturing method of the composition of this invention, a colorant is made into alkali-soluble resin containing the acryl-type copolymer in this invention so that the viscosity after kneading-dispersion process may become a comparatively high viscosity of 10,000 mPa * s or more, Preferably 100,000 mPa * s or more. The kneading and dispersion treatment is carried out, and then the acrylic soluble resin is added, and then the dispersion is carried out so that the viscosity after the microdispersion treatment is relatively low viscosity of 1,000 mPa · s or less, preferably 100 mPa · s or less.

The machines used in the kneading dispersion process are two rolls, three rolls, ball mills, trommills, dispersers, kneaders, corniders, homogenizers, blenders, single screw and twin screw extruders, and are dispersed with strong shearing force. Next, alkali-soluble resin containing a solvent and an acrylic copolymer in the present invention is added, and a glass having a particle size of 0.1 to 1 mm is mainly used using a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like, Microdispersion treatment is performed using beads made of zirconia or the like. It is also possible to omit the kneading dispersion process. In that case, bead dispersion is performed with a pigment, a dispersing agent, or a surface treating agent, and an acrylic copolymer and a solvent in the present invention.

In addition, the details about kneading | mixing and dispersion are T.C. Patton Flow and Pigment Dispersion (published by John Wiley and Sons, 1964).

<Color filter>

The 1st aspect of the color filter of this invention is a color filter whose y value of green (G) in the CIE chromaticity diagram obtained by the photolithographic method using the composition of the said 1st aspect of this invention is 0.59 or more.

As for said y value, 0.59-0.7 are more preferable, and 0.60-0.68 are especially preferable. When y value is too low, the color purity of light will fall and the color reproducibility will become low. On the other hand, there is no restriction | limiting in particular about the x value on CIE chromaticity diagram, Preferably it is 0.2-0.3.

The 2nd aspect of the color filter of this invention is a color filter whose x value of red (R) in CIE chromaticity diagram obtained by the photolithographic method using the composition of the 2nd aspect of this invention is 0.60 or more.

As for said x value, 0.6-0.7 are more preferable, and 0.62-0.68 are especially preferable. When x value is too low, the color purity of light will fall and the problem of color reproducibility will arise. On the other hand, there is no restriction | limiting in particular about the y value on a CIE chromaticity diagram, Preferably it is 0.25-0.35.

The 3rd aspect of the color filter of this invention is a color filter whose y value of blue (B) in the CIE chromaticity diagram obtained by the photolithographic method using the composition of the said 3rd aspect of the present invention is 0.10 or less.

As for the said y value, 0.06-0.1 are more preferable, 0.07-0.095 are especially preferable. When y value is too low, the color purity of light will fall and the color reproducibility will become low. On the other hand, there is no restriction | limiting in particular about the x value on CIE chromaticity diagram, Preferably it is 0.1-0.2.

Here, the CIE chromaticity, that is, the CIE 1964 (10-degree field of view) chromaticity (x value, y value) is measured using a colorimeter (manufactured by Ozka Denshi Co., Ltd.) for an unexposed coating film formed on a glass substrate. It is obtained by measuring.

The composition of the present invention is applied to the substrate through a direct or other layer by a coating method such as spin coating, slit coating, flexible coating, roll coating, or the like to form a coating film of the composition, and a predetermined mask pattern is applied. Each color filter can be manufactured by the photolithographic method which forms the patterned film which consists of a pixel of each color by exposing through light, hardening only the coating film part irradiated with light, and developing with the developing solution.

As radiation used at this time, especially ultraviolet rays, such as g line | wire, h line | wire, and i line | wire, are used preferably.

As a method of manufacturing the color filter of the present invention, a method of forming a coating film by slit coating on a substrate directly or through another layer of the composition of the present invention, and then drying, pattern exposure and alkali development are sequentially performed on the coating film. This is preferred. Thereby, the color filter used for a liquid crystal display element or a solid-state image sensor can be manufactured with little difficulty in a process, high quality, and low cost.

By performing the said alkali developing process, the non-irradiated part is eluted in alkaline aqueous solution by the said exposure, and only the part which photocured remains. Any developer can be used as the developer as long as it dissolves the coating film of the composition of the light unilluminated portion and does not dissolve the light irradiated portion.

Subsequently, after the washing | cleaning removal of the remaining developing solution and drying, it heat-processes (postbaking) at the temperature of 50 degreeC-240 degreeC. The curing coating can be produced by repeating the above steps sequentially for each color. As a result, a color filter is obtained.

Examples of the substrate include alkali-free glass, soda glass, pyrex (registered trademark) glass, quartz glass used in liquid crystal display devices and the like, and transparent conductive films attached thereto, and photoelectric conversion device substrates used in solid state imaging devices. Examples thereof include silicon substrates. Plastic substrates are also possible. On these substrates, a black stripe which normally isolates each pixel is formed.

In addition, the plastic substrate preferably has a gas barrier layer and / or a solvent-resistant layer on its surface.

Drying (prebaking) of the coating film of the composition of this invention apply | coated on the board | substrate can be performed for 10 to 300 second at the temperature of 50 degreeC-140 degreeC in a hotplate, oven, etc.

The coating thickness (after drying) of the coating film of the composition of this invention is generally 0.3-5.0 micrometers, Preferably it is 0.5-3.5 micrometers, Most preferably, it is 1.0-2.5 micrometers.

As the developing solution, any composition can be used as long as it dissolves the composition of the present invention and does not dissolve the light irradiation part. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used.

As an organic solvent, the above-mentioned solvent used when preparing the composition of this invention is mentioned.

As image development temperature, it is 20 degreeC-30 degreeC normally, and as image development time, it is 20 to 90 second.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. The concentration of the alkaline compounds such as roxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001 to 10% by mass, preferably 0.01 to 1 The alkaline aqueous solution melt | dissolved so that it may become mass% is used. Moreover, when using the developing solution which consists of such alkaline aqueous solution, generally, after image development, it wash | cleans (rinses) with water.

Post-baking is post-development heating in order to make hardening perfect, and it heats (hard baking) of about 200 degreeC-220 degreeC normally.

This post-baking process can be performed continuously or batchwise using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the coating film after image development may be in said condition.

Although the use mainly of a color filter was mainly described as a use of the composition of this invention, it is a matter of course that it is applicable also to the black matrix formed between the pixels of a color filter. The black matrix can be formed by photoexposure and alkali development of a composition to which black coloring agents such as carbon black and titanium black are added instead of the coloring agent of the composition of the present invention, and then post-baking to promote curing of the film. .

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

[Example 1]

<< preparation of red (R) photocurable colored resin composition >>

Each component of Table 1 below was stirred and mixed at 3000 rpm for 3 hours with a homogenizer.

(Table 1)

Colorant (Organic Pigment) Pigment Red 254 7 parts by mass Pigment Red 177 10 parts by mass Alkali-soluble resin (BzMA / phosphate monomer / Acr (EO) n) copolymer = 70/20/10 (molar ratio)
Mw (mass average molecular weight): 10000 propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)
14 parts by mass Dispersant 30% solution of mixed solvent of propylene methyl glycol acetate and butyl acetate
10 parts by mass solvent Propylene glycol monomethyl ether acetate

(Description of Symbols Used in the Present Invention)

BzMA: benzyl methacrylate

Phosphoric Acid Group-containing Monomer: CH ₂ = CHCH ₂ CH ₂ CO (OCH ₂ CH ₂ ) P (OH) ₂

Acr (EO) n: CH ₃ (OC ₂ H ₄ ) nOCOC (CH ₃ ) = CH ₂

MAA: methacrylic acid

The mixed solution in which the colorant obtained as described above was dispersed was subjected to microdispersion for 6 hours using a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads.

Furthermore, it disperse | distributed at the flow rate of 500 g / min by the pressure of 2000 kg / cm <3> by the high pressure disperser (brand name: NANO-3000-10, the Nippon-Bui Co., Ltd. product). This treatment was repeated 10 times to obtain a dispersion.

Then, the component of following Table 2 was further added, stirred and mixed, and the photocurable composition for red (R) was prepared.

Table 2

Photopolymerizable compound Dipentaerythritol pentahexaacrylate 12 parts by mass Photopolymerization initiator 4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -S-triazine 2 parts by mass Alkali-soluble resin (only n is different and same as above) (BzMA / phosphate monomer / Acr (EO) n) copolymer = 70/20/10 (molar ratio)
Mw: 10000 propylene glycol monomethyl ether acetate solution
(Solid content: 50 mass%)
25 parts by mass solvent Propylene glycol monomethyl ether acetate 86 parts by mass

"evaluation"

The photocurable composition obtained above was evaluated by the following method, and the result is shown in Table 7.

[CIE Chromaticity (x value, y value), Y value and contrast evaluation]

<Creation of measuring board>

The said photocurable composition was apply | coated so that it might be set to 2.5 micrometers in film thickness on the glass substrate (brand name: 1737 Corning Co., Ltd. product) of 100 mm x 100 mm, and it dried for 60 second (prebaking) in 90 degreeC oven. Subsequently, 200mj / cm <2> exposure (roughness is 20mW / cm <2>) over the whole surface, and the coating film which completed exposure by 1% aqueous solution of alkaline developing solution (brand name: CDK-1, the product made by FUJIFILM Materials) was carried out. Covered and stopped for 60 seconds. Thereafter, pure water was sprayed onto the shower to wash off the developer.

As described above, the coating film subjected to the photocuring treatment and the developing treatment was subjected to heat treatment (post baking) for 1 hour in an oven at 220 ° C., and a colored resin coating film for color filters was formed on the glass substrate.

<Measurement method>

(1) CIE chromaticity (x value, y value) and Y value

CIE chromaticity (x value, y value) was measured using the unexposed coating film formed on the glass substrate, and the y value measured the obtained measurement board | substrate using MCPD-2000 by Ozka Denshi Corporation. The higher the value of the x and y values, the better the color purity and color reproducibility. The higher the Y value, the larger the transmittance.

(2) measurement of contrast

The colored resin coating for color filters was sandwiched on a glass substrate with a polarizing plate, and the polarizing plate was measured with parallel brightness and the linear brightness with (BM-5 Topcon Co., Ltd.). The brightness was obtained.

[Developability evaluation]

A glass substrate (trade name: 1737 Corning Co., Ltd.) having a thickness of 100 mm x 100 mm was applied so as to have a thickness of 2.0 µm, and dried (prebaked) for 60 seconds in a 90 ° C oven. Thereafter, 200 mj / cm 2 of exposure (roughness: 20 mW / cm 2) was performed with a mask having a line width of 20 μm, and a 1% aqueous solution of an alkaline developer (trade name: CDK-1, manufactured by Fujifilm Electronics) was used. It developed at 25 degreeC.

The number of developing seconds remaining after the line width was stabilized was expressed as a developing latitude.

[Spin coat (coating film uniformity)]

30 g of the said photocurable composition (resist liquid) prepared on the glass substrate of 550 mm x 650 mm was dripped at the center, and spin-coated at 600 rpm. The thickness from the edge of the coated substrate to the portion 300 mm inwardly in the diagonal direction was measured. The coating thickness deviation was represented by the following formula and expressed in%.

Thickness deviation = (thickness of center thickness-green part 300mm inside) / thickness of center part

[Slit Coating]

Using a slit coating apparatus having a slit head having a slit interval of 50 μm and an effective coating width of 20 mm, the gap between the slit and the substrate was adjusted so that the coating thickness after drying was 2 μm, and the coating speed of 50 mm / sec was used. The coating liquid of the photocurable composition was apply | coated on the rectangular glass substrate of 230 mm in width, 300 mm in length, and 0.7 mm in thickness, and the coating surface of 21 mm in width and 260 mm in length was obtained. After application, after prebaking at 90 ° C. for 60 seconds on a hot plate, visual observation was performed to count the number of uneven lines on the coating surface. "0", 1-5, "(triangle | delta)", and 6 or more things were evaluated by "x" that the line | surface of the line | surface has no line-like stain at all.

[Examples 2-3]

Instead of using n = 2 alkali-soluble resins of Table 1 and Table 2 in Example 1, except that alkali-soluble resins of n = 4 and n = 9 of Table 7 were used. After performing similarly to 1 and obtaining a photocurable composition, the same evaluation was performed and the result was shown in Table 7.

[Examples 4 to 6]

<< Preparation of green (G) photocurable colored resin composition >>

In Example 1, instead of using the components of Tables 1 and 2, the components of Tables 3 and 4 below were used, and n = 2 shown in Table 7, instead of using an alkali-soluble resin of n = 2. , Green was obtained in the same manner as in Example 1 except that alkali-soluble resins of n = 4 and n = 9 were obtained.

Evaluation similar to Example 1 was performed and the result was shown in Table 7.

(Table 3)

Colorant (Organic Pigment) Pigment Green 7 10 parts by mass Pigment Yellow 150 7 parts by mass Alkali-soluble resin (only n is different and same as above) (BzMA / phosphate monomer / Acr (EO) n) copolymer = 70/20/10 (molar ratio)
Mw: 10000 propylene glycol monomethyl ether acetate solution
(Solid content: 50 mass%)
7 parts by mass Dispersant 30% solution of mixed solvent of propylene methyl glycol acetate and butyl acetate
6 parts by mass solvent Propylene glycol monomethyl ether acetate 85 parts by mass

(Table 4)

Photopolymerizable compound Dipentaerythritol pentahexaacrylate 10 parts by mass Photopolymerization initiator 4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -S-triazine 4 parts by mass Alkali-soluble resin (only n is different and same as above) (BzMA / phosphate monomer / Acr (EO) n) copolymer = 70/20/10 (molar ratio)
Mw: 10000 propylene glycol monomethyl ether acetate solution
(Solid content: 50 mass%)
15 parts by mass solvent Propylene glycol monomethyl ether acetate 40 parts by mass

EXAMPLES 7-9

<< preparation of blue (B) photocurable colored resin composition >>

In Example 1, instead of using the components of Tables 1 and 2, the components of Tables 5 and 6 below were used, and instead of using the alkali-soluble resin of n = 2, It carried out similarly to Example 1 except having used each alkali-soluble resin of = 2, n = 4, n = 9, and obtained the blue (B) photocurable composition.

Evaluation similar to Example 1 was performed and the result was shown in Table 7.

(Table 5)

Colorant (Organic Pigment) Pigment Blue 15: 6 10 parts by mass Pigment Violet 23 2 parts by mass Alkali-soluble resin (only n is different and same as above) (BzMA / phosphate monomer / Acr (EO) n) copolymer = 70/20/10 (molar ratio)
Mw: 10000 propylene glycol monomethyl ether acetate solution
(Solid content: 50 mass%)
10 parts by mass Dispersant 30% solution of mixed solvent of propylene methyl glycol acetate and butyl acetate
10 parts by mass solvent Propylene glycol monomethyl ether acetate 78 parts by mass

(Table 6)

Photopolymerizable compound Dipentaerythritol pentahexaacrylate 20 parts by mass Photopolymerization initiator 4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -S-triazine 2 parts by mass Alkali-soluble resin (only n is different and same as above) (BzMA / phosphate monomer / Acr (EO) n) copolymer = 70/20/10 (molar ratio)
Mw: 10000 propylene glycol monomethyl ether acetate solution
(Solid content: 50 mass%)
48 parts by mass solvent Propylene glycol monomethyl ether acetate 100 parts by mass

[Comparative Example 1]

In Example 1, red as in Example 1 except that the alkali-soluble resin (copolymer) (BzMA / phosphate-containing monomer) copolymer = 80/20 (molar ratio) and Mw (weight average molecular weight) = 10,000 were used. The photocurable composition for (R) was prepared.

[Comparative Example 2]

In Example 4, green (G) was used in the same manner as in Example 4 except that the alkali-soluble resin (copolymer) (BzMA / phosphate-containing monomer) copolymer = 80/20 (molar ratio) and Mw = 10,000 was used. The photocurable composition was prepared.

[Comparative Example 3]

In Example 7, the photocurable composition for blue (B) was prepared in the same manner as in Example 7 except that the alkali-soluble resin (copolymer) (BzMA / phosphate-containing monomer) copolymer = 80/20 and Mw = 10,000 was used. Prepared.

[Comparative Example 4]

In Example 1, the photocurable composition for red (R) was prepared in the same manner as in Example 1 except that the alkali-soluble resin (copolymer) (BzMA / phosphate-containing monomer) copolymer = 80/20 and Mw = 10,000 was used. Prepared.

[Comparative Example 5]

In Example 4, the photocurable composition for green (G) was prepared like Example 4 except having used BzMA / MAA = 80/20 and Mw = 10,000 as alkali-soluble resin (copolymer).

[Comparative Example 6]

In Example 7, the photocurable composition for blue (B) was used in the same manner as in Example 7 except that the alkali-soluble resin (copolymer) used (BzMA / MAA) copolymer = 80/20 (molar ratio) and Mw = 10,000. Prepared.

[Comparative Example 7]

In Example 1, the alkali-soluble resin (copolymer) was used in the same manner as in Example 1 except that (BzMA / MAA / Acr (EO) n) copolymer = 70/20/10 (molar ratio) and Mw = 10,000 were used. A red (R) photocurable composition was prepared.

Comparative Example 8

In Example 4, the alkali-soluble resin (copolymer) was used in the same manner as in Example 4 except that (BzMA / MAA / Acr (EO) n) copolymer = 70/20/10 (molar ratio) and Mw = 10,000 were used. Green (G) photocurable composition was prepared.

Comparative Example 9

In Example 7, the alkali-soluble resin (copolymer) was used in the same manner as in Example 7, except that (BzMA / MAA / Acr (EO) n) copolymer = 70/20/10 (molar ratio) and Mw = 10,000 were used. Blue (B) photocurable composition was prepared.

(Table 7)

As can be seen from Table 7, in Comparative Examples 1 to 6, the coating property (spin coat coating film uniformity, slit coating stain) was poor, and in Comparative Examples 7 to 9, the developing property was not sufficient. On the other hand, in all of the examples, good results were obtained.

ADVANTAGE OF THE INVENTION According to this invention, the photocurable colored resin composition which is for color filters excellent in developability, color reproducibility, and contrast, and which dispersibility of a coloring agent is good can be provided.

Moreover, according to this invention, the color filter excellent in developability, color reproducibility, and contrast can be provided.

Moreover, when the photocurable composition of this invention is used, even if it is thin and contains a coloring agent in comparatively high concentration, the color filter excellent in color reproducibility and contrast can be obtained, without impairing developability and adhesiveness with a board | substrate.

Therefore, as the film thickness of the color filter becomes thinner, not only the color reproducibility and the decrease in the contrast due to the decrease in the optical density can be prevented, but also the color filter having better color reproducibility and contrast than the conventional color filter can be obtained. .

When this characteristic which the photocurable composition of this invention has is represented numerically, when the film thickness of a color filter is x micrometer and the content rate of the colorant in a color filter is y mass%, the value of xxy = A is a value more than a specific value. It is possible to keep as. For example, in the case of green (G), the value of A can be 111 or more, preferably 120 or more, 105 or more if red (R), preferably 100 or more, and 51 or more if blue (B). Preferably, 57 or more color filters can be obtained.

This feature which cannot be predicted by the conventional photocurable composition is presumed to mainly affect that alkali-soluble resin in the photocurable composition of this invention improves alkali solubility, dispersibility of a coloring agent, and adhesiveness to a board | substrate.

Claims (9)

In the photocurable composition containing a coloring agent, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, The said alkali-soluble resin is an acryl-type copolymer which uses a phosphate group containing monomer and an alkylene oxide chain containing monomer as a copolymerization monomer component, The said coloring agent is a pigment for green (G), The said in the non volatile matter of the said photocurable composition. The content rate of a coloring agent is 38 mass% or more, The alkylene oxide chain-containing monomer is a polyalkylene oxide chain-containing (meth) acrylate monomer represented by the following general formula (1).

[In General formula (1), R <^3> represents a hydrogen atom or a methyl group. (EO) _n represents a polyoxyethylene chain, (PO) _m represents a polyoxypropylene chain, and (BO) ₁ represents a polyoxybutylene chain. n represents the integer of 2-20, m and l represent the integer of 0-10, respectively. However, 2≤ (m + n + l) ≤30. R <^4> represents a hydrogen atom, a C1-C12 linear or branched alkyl group. (EO) _n , (PO) _m and (BO) _l may be combined in any order.] In the photocurable composition containing a coloring agent, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, Said alkali-soluble resin is an acryl-type copolymer which uses a phosphate group containing monomer and an alkylene oxide chain containing monomer as a copolymerization monomer component, The said coloring agent is a pigment for red (R), and the said in the non volatile matter of the said photocurable composition. The content rate of a coloring agent is 35 mass% or more, The alkylene oxide chain-containing monomer is a polyalkylene oxide chain-containing (meth) acrylate monomer represented by the following general formula (1).

[In General formula (1), R <^3> represents a hydrogen atom or a methyl group. (EO) _n represents a polyoxyethylene chain, (PO) _m represents a polyoxypropylene chain, and (BO) ₁ represents a polyoxybutylene chain. n represents the integer of 2-20, m and l represent the integer of 0-10, respectively. However, 2≤ (m + n + l) ≤30. R <^4> represents a hydrogen atom, a C1-C12 linear or branched alkyl group. (EO) _n , (PO) _m and (BO) _l may be combined in any order.] In the photocurable composition containing a coloring agent, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, Said alkali-soluble resin is an acryl-type copolymer which uses a phosphate group containing monomer and an alkylene oxide chain containing monomer as a copolymerization monomer component, The said coloring agent is a pigment for blue (B), and the said in the non volatile matter of the said photocurable composition. The content rate of a coloring agent is 17 mass% or more, The alkylene oxide chain-containing monomer is a polyalkylene oxide chain-containing (meth) acrylate monomer represented by the following general formula (1).

[In General formula (1), R <^3> represents a hydrogen atom or a methyl group. (EO) _n represents a polyoxyethylene chain, (PO) _m represents a polyoxypropylene chain, and (BO) ₁ represents a polyoxybutylene chain. n represents the integer of 2-20, m and l represent the integer of 0-10, respectively. However, 2≤ (m + n + l) ≤30. R <^4> represents a hydrogen atom, a C1-C12 linear or branched alkyl group. (EO) _n , (PO) _m and (BO) _l may be combined in any order.] delete delete delete The y value of green (G) in the CIE chromaticity diagram obtained by the photolithographic method using the photocurable composition of Claim 1 is 0.59 or more, The color filter characterized by the above-mentioned. The x value of red (R) in the CIE chromaticity diagram obtained by the photolithographic method using the photocurable composition of Claim 2 is 0.60 or more, The color filter characterized by the above-mentioned. The y value of blue (B) in the CIE chromaticity diagram obtained by the photolithographic method using the photocurable composition of Claim 3 is 0.10 or less, The color filter characterized by the above-mentioned.