KR102041207B1 - Colored curable composition, color filter, method of producing the same, solid state imaging device, liquid crystal display device, and pigment polymer - Google Patents

Abstract

(Problem) Provides the colored curable composition containing the dye multimer which is excellent in color purity, light resistance, heat resistance, and solvent resistance, little color conversion, and can form a cured film with favorable pattern moldability.
(Solution means) The colored curable composition containing (a) the dye multimer which contains a xanthene skeleton as a partial structure of a pigment | dye site | part, (b) polymeric compound, (c) photoinitiator, and (d) organic solvent.

Description

Colored curable composition, color filter, its manufacturing method, solid-state image sensor, liquid crystal display device, and dye multimer {COLORED CURABLE COMPOSITION, COLOR FILTER, METHOD OF PRODUCING THE SAME, SOLID STATE IMAGING DEVICE, LIQUID CRYSTAL DISPLAY DEVICE, AND PIGMENT POLYMER }

This invention relates to the coloring curable composition suitable for manufacture of the color filter used for a liquid crystal display device, a solid-state image sensor, etc., a color filter, its manufacturing method, a solid-state image sensor, a liquid crystal display device, and a dye multimer.

As one of the methods of manufacturing the color filter used for a liquid crystal display device, a solid-state image sensor, etc., there is a pigment dispersion method. As this pigment dispersion method, it uses the colored curable composition which disperse | distributed the pigment to various photosensitive compositions, and is colored by the photolithographic method. There is a method of making a filter. That is, a colored pixel is obtained by apply | coating a colored curable composition on a board | substrate using a spin coater, a roll coater, etc., drying, forming a coating film of a colored curable composition, pattern exposing and developing the said coating film. This operation is repeated for a desired color to produce a color filter.

Since the method uses a pigment, it is stable to light and heat, and is patterned by the photolithography method. Thus, the positional accuracy is sufficiently secured, and has been widely used as a preferable method for the production of color filters for liquid crystal display devices.

On the other hand, in the color filter for solid-state image sensors, such as CCD, in recent years, higher definition is desired. Although the pattern size tends to be finer with high definition, it is considered difficult in the pigment dispersion method, which has been widely used in the past, to further reduce the size of the pattern to further improve the resolution. One reason is that coarse particles formed by aggregation of pigment particles in a fine pattern cause color irregularities. Therefore, recently, the pigment dispersion method which has been used universally until now has become a situation that is not very suitable for the use which requires a fine pattern, such as a solid-state image sensor.

In order to achieve high definition and high resolution under the said background, using dye as a coloring agent is examined conventionally (for example, refer patent document 1). However, dye-containing colored curable compositions have new problems shown below. In other words,

(1) Dye in the state of molecular dispersion is generally inferior in light resistance and heat resistance compared with the pigment which is a molecular aggregate.

(2) The dye in the state of molecular dispersion is generally poor in solvent resistance compared to the pigment which is a molecular aggregate.

(3) The dye often shows interaction with other components in the colored curable composition, and it is difficult to control the solubility (developability) of the hardened part and the uncured part.

(4) When the molar extinction coefficient (ε) of the dye is low, a large amount of dye must be added. Therefore, other components such as a polymerizable compound (monomer), a binder, and a photopolymerization initiator in the colored curable composition must be reduced. The curability of a colored curable composition, the heat resistance after hardening, the developability after exposure, etc. fall.

Among these problems that dyes have, (4) xanthenes (for example, refer to Patent Document 2) as dyes that solve the molar extinction coefficient (ε) of dyes, but compounds having lower light resistance and heat resistance than other dyes In many cases, the improvement is strongly desired.

Moreover, the coloring curable composition containing dye has the problem of color conversion other than the above-mentioned problem. For example, in order to form a red pixel on the formed green pixel, the coloring curable composition containing red dye is apply | coated on a green pixel, and image development removes the unexposed red curable composition layer on a green pixel, and dye in a green pixel is carried out. Is easily eluted to the red curable composition, or the dye in the red colored curable composition shifts to the green pixel, causing the green pixel to discolor or discolor, or the green pixel to be reddish. This is strongly desired.

In addition, in the colored curable composition containing the dye, the dye is liable to be sublimated in addition to the heat resistance problems of the dye when the colored pixel receives heat during the manufacturing process of the color filter for forming the colored pixel, the process of installing the color filter in a solid-state image sensor, or the like. In addition, there is a problem that the colored pixels are discolored and discolored by dye sublimation, so that a desired color cannot be obtained, and there is also a problem that the manufacturing process is contaminated by the sublimed dye. As a technique for preventing this, it is proposed to use a dye provided with a polymerizable group in a colored curable composition (see, for example, Patent Document 3), but a sufficient effect is not obtained with respect to the above-described color conversion, and further, Improvement was desired.

Japanese Patent Laid-Open No. 6-75375 Japanese Patent Publication No. 2010-32999 Japanese Patent Laid-Open No. 2000-162429

More excellent light resistance and heat resistance were calculated | required by the colored curable composition containing xanthenes as a dye. In addition, as described in the above problem (2), in order to use the dye as a coloring component, it was required to improve solvent resistance.

Solvent resistance is the performance which the coloring component in a hardening part does not elute in a solvent, but is retained in a colored pixel. When manufacturing an RGB color filter by the photolithographic method, in order to form the pattern of each color sequentially, a coloring pattern is covered with the coloring curable composition from which a color differs. In that case, when the coloring component in a hardening part elutes into the colored curable composition of a next color, or when the dye contained in the colored curable composition of a next color shifts to a colored pixel, a problem of mixed color arises, and it hardens in a color filter manufacturing process. Wealth requires high solvent resistance. In this respect, the dye is in the state of molecular dispersion, and the solvent resistance is inferior to that of the pigment forming the aggregate with strong intermolecular force.

Moreover, in manufacture of a color filter, since heat processing may be performed in order to raise the hardening | curing degree of a coloring pattern after an application | coating, exposure, and image development process, the fixability of dye in a hardening part also becomes a problem. Since the dye in the molecular dispersion state can move with a small thermal energy compared with the pigment which is a molecular aggregate, it is easy to color-convert to the adjacent pattern whose color differs, and fixation of the dye in a hardening part was a big subject.

This invention is made | formed in view of the said problem, and makes it a subject to achieve the following objectives.

That is, the 1st objective of this invention is to provide the coloring curable composition containing the dye multimer which is excellent in color purity, light resistance, heat resistance, solvent resistance, little color conversion, and can form a cured film with favorable pattern moldability. have.

Further, a second object of the present invention is to provide a color filter having a color pattern excellent in color purity, heat resistance, and light resistance even when thinned, a manufacturing method of the color filter, a solid-state imaging device including the color filter, and a liquid crystal display device. It is to offer.

Moreover, the 3rd objective of this invention is providing the dye multimer which is excellent in color purity, light resistance, heat resistance, solvent resistance, little color conversion, and can form the colored curable composition with favorable pattern moldability.

MEANS TO SOLVE THE PROBLEM The present inventors examined the various pigment | dye in detail, and, as a result, the xanthene compound which has a specific structure has a favorable color and high absorption coefficient, and introduce | transduces the said xanthene skeleton into a dye multimer, especially a polymeric group in a xanthene skeleton By introducing into a dye multimer as a polymerization component, it is possible to provide a colored curable composition which has high solvent resistance and can reduce the color conversion, and also introduces an alkali-soluble group into the dye multimer as necessary to form a pattern. The knowledge that this excellent (small concentration dependence of alkaline developing solution) can be provided can be provided, and this invention was achieved based on this knowledge.

The specific means for solving the said subject is as follows.

<1> The colored curable composition containing the (a) dye multimer which contains a xanthene skeleton as a partial structure of a pigment | dye site | part, (b) polymeric compound, (c) photoinitiator, and (d) organic solvent.

<2> The colored curable composition according to <1>, wherein the xanthene skeleton is a dye skeleton derived from a xanthene compound represented by the following General Formula (M).

[In General Formula (M), R <^1> , R <^2> , R <^3> , and R <^4> represent a hydrogen atom or a monovalent substituent each independently, R <^5> represents a monovalent substituent each independently, m is 0-5 Represents an integer]

<3> In <1> or <2>, the said (a) dye multimer contains at least one of structural units represented by the following general formula (A), general formula (B), or general formula (C). The colored curable composition which is obtained or is a dye multimer represented by general formula (D).

[In formula (A), X <^1> represents the coupling group formed by superposition | polymerization, L <^1> represents a single bond or a bivalent coupling group, and Dye represents the pigment | dye residue remove | excluding ^one arbitrary hydrogen atom from the said general formula (M). Indicates]

[In Formula (B), X <^2> represents the coupling group formed by superposition | polymerization, L <^2> represents a single bond or a bivalent coupling group, A represents the group which can be ion-bonded or coordinate-bonded with Dye, and Dye is the said General formula ( A dye residue capable of ionic or coordinating with A by removing one hydrogen atom from M)]

[L <^3> shows a single bond or a bivalent coupling group in general formula (C), and when two or more L <^3> exists, the structure of L <^3> may be same or different. Dye represents the pigment | dye residue remove | excluding two arbitrary hydrogen atoms from the said General formula (M). n3 represents an integer of 1 to 4]

[L ⁴ in General Formula (D) represents an n4 valent linking group, n ⁴ represents an integer of 2 to 100, and a plurality of Dyes are each independently a dye residue from which one arbitrary hydrogen atom is removed from General Formula (M). Indicates]

<4> The colored curable composition according to any one of <1> to <3>, wherein the dye multimer (a) further has an alkali-soluble group.

<5> The colored curable composition according to any one of <1> to <4>, wherein the photopolymerization initiator (c) is an oxime compound.

<6> Color filter which uses the colored curable composition in any one of <1>-<5>.

<7> The manufacturing method of the color filter which apply | coats the coloring curable composition in any one of <1>-<5> to a board | substrate, exposes through a mask, and develops and forms a pattern shape.

<8> Solid-state image sensor provided with the color filter as described in <6>.

<9> The liquid crystal display device provided with the color filter as described in <6>.

<10> A dye multimer comprising a dye skeleton derived from a xanthene compound represented by the following General Formula (M) as a partial structure of a dye portion.

[In General Formula (M), R <^1> , R <^2> , R <^3> , and R <^4> represent a hydrogen atom or a monovalent substituent each independently, R <^5> represents a monovalent substituent each independently, m is 0-5 Represents an integer]

In formula (D), n4 represents an integer of 2 to 100,

L ⁴ is

when n4 is 2, a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic linking group, -CH = CH —, —O—, —S—, —NR— (R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), —C (═O) —, —SO—, —SO ₂ —, and these Represents a divalent linking group selected from the group consisting of two or more linking groups formed,

When n4 is 3 or more, 3 ~ which is formed by making a substituted or unsubstituted arylene group, a substituted or unsubstituted heterocyclic linking group, or a substituted or unsubstituted alkylene linking group as the central mother nucleus, and the divalent linking group is substituted. Dye multimer which shows a 100-valent coupling group.

According to the present invention, the pixel pattern is formed into a thin film (for example, 1 µm or less in thickness), and the high definition of a micro-size of 2 µm or less (the variation of the pixel pattern viewed from the substrate normal direction, for example, 0.5 to 2.0 µm) It is particularly effective for forming a color filter for a solid-state image sensor, which is required and requires a good rectangular cross-sectional profile.

ADVANTAGE OF THE INVENTION According to this invention, the coloring curable composition containing the dye multimer which is excellent in color purity, light resistance, heat resistance, and solvent resistance, has little color conversion, and can form a favorable pattern moldability can be provided.

Moreover, even when it is thin, the color filter which has the coloring pattern excellent in color purity, heat resistance, and light resistance, the manufacturing method of the said color filter, the solid-state image sensor provided with the said color filter, and a liquid crystal display device can be provided.

Moreover, the dye multimer which is excellent in color purity, light resistance, heat resistance, solvent resistance, little color conversion, and can form the colored curable composition with favorable pattern moldability can be provided.

Hereinafter, the coloring curable composition, the color filter, the manufacturing method of a color filter, a solid-state image sensor, a liquid crystal display device, and a dye multimer of this invention are demonstrated in detail. Although description of the element | module described below may be made | formed based on typical embodiment of this invention, this invention is not limited to such embodiment. In addition, the numerical range shown using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

The colored curable composition of this invention contains the dye multimer which contains (a) xanthene frame | skeleton as a partial structure of a pigment | dye site | part, (b) polymeric compound, (c) photoinitiator, and (d) organic solvent, It is characterized by the above-mentioned. It is done.

The dye multimer which contains (a) xanthene skeleton used for the colored curable composition of this invention as a partial structure of a pigment | dye site | part is demonstrated.

`` (A) Dye multimer containing xanthene skeleton as a partial structure of the dye site ''

The dye multimer in this invention is a dye multimer which contains the xanthene skeleton demonstrated in detail below as a partial structure of a pigment | dye site | part. The method of introducing a xanthene skeleton into the dye multimer of the present invention is arbitrary, and a polymer may be obtained by polymerizing or copolymerizing the introduction of a xanthene skeleton into a polymerizable monomer, or after forming a multimer, a polymer reaction or the like. You may introduce a xanthene skeleton by this.

As a preferable aspect, the multimer containing at least 1 structural unit represented by the said General formula (A), General formula (B), or General formula (C), or the dye multimer represented by the said General formula (D) Can be mentioned.

<Preferred Physical Properties of the Dye Multimer in the Present Invention>

Since the dye multimer in this invention can form the cured film excellent in color purity, light resistance, heat resistance, and solvent resistance, little color conversion, and pattern moldability, it can be used for the color curable composition suitable for color pattern formation of a color filter. Can be. From such a viewpoint, when the pigment multimer in this invention is given the preferable physical property in this invention, when applying the dye multimer in this invention to a colored curable composition, it is a dye multimer in this invention from a viewpoint of improving coloring pattern formability. It is preferable to have an alkali-soluble group.

Although there is no restriction | limiting in particular as a method of introduce | transducing an alkali-soluble group into the dye multimer in this invention, It can introduce | transduce by synthesizing a dye multimer using the monomer which has an alkali-soluble group, or it is alkali-soluble after synthesize | combining a dye multimer. Groups can be introduced.

When synthesize | combining a dye multimer using the monomer which has an alkali-soluble group, The dye multimer which contains at least one of the structural unit represented by the said General formula (A), General formula (B), or General formula (C), Or at least 1 sort (s) of the dye multimer represented by the said general formula (D) should just have alkali-soluble group. When the structural unit represented by the said general formula (A), general formula (B), or general formula (C) is a monomer which has alkali-soluble group, you may have alkali-soluble group in Dye part (color moiety). From a viewpoint of synthetic suitability, it is preferable that at least 1 sort (s) of the other ethylenically unsaturated bond containing monomer contained as a copolymerization component rather than the monomer which forms the structural unit which has a Dye part (color moiety) is a monomer which has an alkali-soluble group.

As a preferable alkali-soluble group which the dye multimer in this invention has, it is a carboxyl group, a sulfonic acid group, a phosphonic acid group, a hydroxyl group, a sulfonimide group, Preferably it is a carboxyl group and a sulfonic acid group.

Moreover, as a preferable example of the other ethylenically unsaturated bond containing monomer contained as a copolymerization component of the said dye multimer, Monocarboxylic acid, such as acrylic acid, methacrylic acid, crotonic acid, (alpha) -methyl- p-carboxystyrene; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid, methacrylicoxyethylphosphonic acid, styrenesulfonic acid, p-hydroxystyrene and the like, and acrylic acid and methacrylic acid are preferred.

It is preferable to contain the acid value 10-400 mgKOH / g, and, as for the dye multimer in this invention from the viewpoint of the coloring pattern formation property at the time of applying to a colored curable composition, it is more preferable to contain the acid value 30-300 mgKOH / g, It is more preferable to contain an acid value of 50-200 mgKOH / g.

In the present invention, the acid value is determined by the method described in JIS Standard (JIS K 0070: 1992).

It is preferable that the solubility to alkaline solution (pH9-15) is 0.1 mass% or more and 80 mass% or less, as for the dye multimer in this invention, it is more preferable that it is 0.5 mass% or more and 50 mass% or less, and it is 1 mass% or more It is more preferable that it is 30 mass% or less. By being in this area | region, when using the dye multimer of this invention for the use which requires alkali image development, such as a colored curable composition, it becomes possible to form a preferable shape and to reduce the residue on a board | substrate.

It is preferable to melt | dissolve the dye multimer in this invention in the following organic solvents. As the organic solvent, esters (for example, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, etc.), ethers (for example, methyl cellosolve acetate) , Ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc., ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), aromatic hydrocarbons (e.g., Toluene, xylene, etc.) are mentioned, It is preferable to melt | dissolve 1 mass% or more and 50 mass% or less with respect to these solvents, More preferably, they are 5 mass% or more and 40 mass% or less, More preferably, 10 mass% It is preferable that it is more than 30 mass%. By being in this area | region, when apply | coating the dye multimer in this invention to a coloring curable composition etc., it becomes possible to reduce the density | concentration fall by elution after obtaining a coated surface shape and application of a colored curable composition of a different color.

It is preferable that it is 50 degreeC or more, and, as for Tg of the dye multimer in this invention, it is more preferable that it is 100 degreeC or more. Moreover, it is preferable that the 5% mass reduction temperature by thermal mass spectrometry (TGA measurement) is 120 degreeC or more, It is more preferable that it is 150 degreeC or more, It is further more preferable that it is 200 degreeC or more. By being in this area | region, it becomes possible to reduce the density | concentration change resulting from the heating process at the time of applying the dye multimer in this invention to a colored curable composition etc.

It is preferable that the maximum absorption wavelength ((lambda) max) of the dye multimer in this invention is 510 nm or more and 590 nm or less, It is preferable that it is 530 nm or more and 570 nm or less, It is more preferable that it is 540 nm or more and 555 nm or less. By being in this area, when applied to a colored curable composition or the like, a color filter having good color reproducibility can be produced. Moreover, it is preferable that the absorbance of the maximum absorption wavelength ((lambda) max) is 1,000 times or more with respect to the absorbance in 450 nm of the dye multimer of this invention, It is more preferable that it is 10,000 times or more, It is further more preferable that it is 100,000 times or more. By this ratio being in this range, when applying the dye multimer of this invention to a coloring curable composition etc., especially when manufacturing a blue color filter, a color filter with a higher transmittance | permeability can be formed.

The extinction coefficient per unit mass of the dye multimer in the present invention (hereinafter referred to as ε '. Ε' = ε / average molecular weight, unit: L / g · cm) is preferably 30 or more, more preferably 60 or more. It is preferable and it is more preferable that it is 100 or more. When it is in this range, when the dye multimer in this invention is applied to a colored curable composition, and a color filter is produced, the color filter with a good color reproducibility can be produced.

Moreover, it is more preferable that the dye multimer in this invention simultaneously satisfy | fills the preferable range of the maximum absorption wavelength ((lambda) max) and the absorption coefficient per unit weight of the said dye multimer.

As a preferable molecular weight of the dye multimer in this invention, it is 3,000-100,000, 4,000-50,000 are more preferable, 5,000-20,000 are more preferable. By being in this range, the effect of this invention can be exhibited unfortunately, the solubility to a solvent is favorable, and the film | membrane (colored pixel) of the colored curable composition obtained by hardening has favorable light resistance, heat resistance, and solvent resistance.

<Structure of Dye Multimer in the Present Invention>

Below, the detail of the structure of the dye multimer in this invention is described.

The dye multimer in this invention contains a xanthene skeleton as a partial structure of a pigment | dye site | part.

It is preferable that the said dye multimer in this invention is a pigment | skeleton frame | skeleton derived from the xanthene compound represented by the following general formula (M).

<Xanthene compound represented by general formula (M)>

The preferable form of the dye multimer in this invention is a dye multimer which contains the pigment skeleton derived from the xanthene compound represented by following General formula (M) as a partial structure of a pigment | dye site | part.

In general formula (M), R <^1> , R <^2> , R <^3> and R <^4> represent a hydrogen atom or a monovalent substituent each independently, R <^5> represents a monovalent substituent each independently, m is an integer of 0-5 Indicates.

As a monovalent substituent in the case where R <^1> -R <^4> and R <^5> in the said general formula (M) represent a monovalent substituent, it is a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), for example. And an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t- Butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-Adaman Tyl group), Alkenyl group (preferably C2-C18, More preferably, they are C2-C18 alkenyl group, For example, a vinyl group, an allyl group, 3-buten- 1-yl group), an aryl group (preferably Preferably it is a C6-C48, More preferably, it is a C6-C24 aryl group, For example, a phenyl group, a naphthyl group, Heterocyclic group ( Preferably it is a C1-C32 heterocyclic group, More preferably, it is a C1-C18 heterocyclic group, For example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group , 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group, silyl group (preferably C3-C38, more preferably C3-C18) Silyl group, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group ( Preferably it is a C1-C48, More preferably, it is a C1-C24 alkoxy group, For example, a methoxy group, an ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxy group , A dodecyloxy group, a cycloalkyloxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group, an aryloxy group (preferably having 6 to 48 carbon atoms, Most preferably, they are C6-C24 aryloxy group, For example, a phenoxy group, 1-naphthoxy group, Heterocyclic oxy group (preferably C1-C32, More preferably, it is C1-C18) Heterocyclic oxy group, for example, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group),

Silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, trimethylsilyloxy group, t-butyldimethylsilyloxy group, diphenylmethylsilyloxy group) , An acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, an acetoxy group, pivaloyloxy group, benzoyloxy group, dodecanoyloxy group), An alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, an ethoxycarbonyloxy group, t-butoxycarbonyloxy group, Cycloalkyloxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy, an aryloxycarbonyloxy group (preferably C7-32, More preferably, C7-24 aryloxycarbon) It is a silyloxy group, For example, phenoxycarbonyloxy), Carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group, sulfamoyloxy group (preferably sulfayloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms). , N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group, alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms), for example , Methylsulfonyloxy group, hexadecylsulfonyloxy group, cyclohexylsulfonyloxy group),

Arylsulfonyloxy group (preferably C6-C32, more preferably C6-C24 arylsulfonyloxy group, for example, phenylsulfonyloxy group), acyl group (preferably C1-C48) Preferably they are acyl groups of 1 to 24 carbon atoms, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably 2 to 48 carbon atoms) More preferably, they are a C2-C24 alkoxycarbonyl group, For example, a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyl oxycarbonyl group, a cyclohexyloxycarbonyl group, 2, 6- di-tert- butyl- 4-methyl cyclohexyl Oxycarbonyl group), aryloxycarbonyl group (preferably aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxycarbonyl group), and carbamoyl group (preferably carbon 1-48, More preferably, it is a C1-C24 carbamoyl group, For example, a carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N -Dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably carbon number) 32 or less, more preferably an amino group having 24 or less carbon atoms, for example, an amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, cyclohexylamino group),

An anilino group (preferably a 6 to 32 carbon atoms, more preferably a 6 to 24 anilino group, for example, an anilino group, an N-methylanilino group) and a heterocyclic amino group (preferably C 1) It is -32, More preferably, it is a 1-18 heterocyclic amino group, For example, 4-pyridylamino group, Carbonamide group (preferably C2-C48, More preferably, it is 2-24 carbon) Amide group, for example, acetamide group, benzamide group, tetradecanamide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferably C1-C32, more preferably C1-C1) It is -24 ureido group, For example, it is a ureido group, N, N- dimethyl ureido group, N-phenyl ureido group, an imide group (preferably carbon number 36 or less, More preferably, it is an imide group of 24 or less carbon atoms). For example, N-succinimide group, N-phthalimide group) , Alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycar A carbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamino group), an aryloxy carbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms), For example, a phenoxycarbonylamino group) and a sulfonamide group (preferably a C1-C48, more preferably a C1-C24 sulfonamide group, For example, a methane sulfonamide group and a butane sulfonamide group) , Benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group) sulfamoylamino group (preferably carbonyl 1 to 48, more preferably sulfamoyl having 1 to 24 carbon atoms) It is a mino group, For example, N, N- dipropyl sulfamoylamino group, N-ethyl-N-dodecyl sulfamoylamino), Azo group (preferably C1-C32, More preferably, it is C1-C24) Azo group, for example, phenylazo group, 3-pyrazolyl azo group),

Alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthi Ogi (preferably an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, a phenylthio group) and a heterocyclic thi group (preferably 1 to 32 carbon atoms), more preferably It is a C1-C18 heterocyclic thi group, For example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyl tetrazolylthio group, the alkylsulfinyl group (preferably C1-C32, More preferably, it is a C1-C24 alkylsulfinyl group, For example, a dodecanesulfinyl group, an arylsulfinyl group (preferably C6-C32, More preferably, it is a C6-C24 arylsulfinyl group, For example, a phenylsulfinyl group, an alkylsulfonyl group (preferably C1-C48, beam) Preferably it is a C1-C24 alkylsulfonyl group, For example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, Octylsulfonyl group, cyclohexylsulfonyl group) and arylsulfonyl group (preferably arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms), for example, phenylsulfonyl group and 1-naphthylsulfonyl group ), Sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, for example, a sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N- Dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group, sulfo group, phosphonyl group (preferably a C1-C32, more preferably a C1-C24 force) Phenyl group, For example, a phenoxy phosphonyl group, an octyloxy phosphonyl group, phenyl phospho Fonyl), phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, diethoxyphosphinoylamino group, dioctyloxyphosphinoylamino group) Can be mentioned.

If the formula (M) in case of R ¹ is further optionally substituted group represented by a monovalent substituent ~R ⁵ it has may have a substituent explained in R ¹ ~R ⁵ further, have two or more substituents these substituents include It may be the same or different.

When R ¹ and R ² , R ³ and R ⁴ , and m in General Formula (M) are 2 or more, each of R ⁵ independently combine with each other to form a 5-, 6-, or 7-membered saturated ring or an unsaturated ring. May be formed. When the 5-membered, 6-membered, or 7-membered ring formed is a group which can be substituted, the substituents described above may be substituted with the substituents described in R ¹ to R ⁵ , and when substituted with two or more substituents, these substituents may be the same or different. good.

In the general formula (M), when R ¹ and R ² , R ³ and R ⁴ , and m are 2 or more, each of R ⁵ independently bonds with each other to form a 5-, 6-, or 7-membered saturated ring having no substituent. Or a 5-, 6- or 7-membered saturated ring having no substituent when forming an unsaturated ring, or an unsaturated ring, for example, a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, A triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, Preferably, a benzene ring, a pyridine ring Can be mentioned.

The molar extinction coefficient of the compound having a xanthene skeleton represented by the general formula (M) is preferably as large as possible from the viewpoint of the film thickness. The maximum absorption wavelength? Max is preferably 520 nm to 580 nm, and more preferably 530 nm to 570 nm from the viewpoint of color purity improvement. In addition, a maximum absorption wavelength and molar extinction coefficient are measured with the spectrophotometer UV-2400PC (made by Shimadzu Corporation).

The melting point of the compound having a xanthene skeleton represented by the general formula (M) is preferably a method in which the melting point is not too high from the viewpoint of solubility.

The compound which has a xanthene skeleton represented by the said general formula (M) can be synthesize | combined by the method as described in literature. Specifically, the method described in tetrahedron letters, 2003, vol. 44, No. 23, pages 4355-4360, tetrahedron, 2005, vol. 61, No. 12, pages 3097 to 3106, etc., may be applied. Can be.

The more preferable dye multimer in this invention is demonstrated.

As a dye multimer which contains a xanthene skeleton as a partial structure of a pigment | dye site | part, the dye multimer containing at least one of structural units represented by the following general formula (A), general formula (B), or general formula (C), Or the dye multimer represented by general formula (D) is mentioned. These will be described sequentially.

<Structural unit represented by general formula (A)>

In General Formula (A), X ¹ represents a linking group formed by polymerization, L ¹ represents a single bond or a divalent linking group, and Dye represents a dye residue obtained by removing one hydrogen atom from the general formula (M). Indicates.

In General Formula (A), X ¹ represents a linking group formed by polymerization. That is, it points to the part which forms the repeating unit corresponding to the main chain formed by a polymerization reaction. In addition, the site | part inserted by two * becomes a repeating unit. Examples of X ¹ include a linking group formed by polymerizing a substituted or unsubstituted unsaturated ethylene group, a linking group formed by ring-opening polymerization of a cyclic ether, and a linking group formed by polymerizing an unsaturated ethylene group. Although the coupling group etc. which are shown specifically below are mentioned, the coupling group formed by superposition | polymerization in this invention is not limited to these.

In addition, in following (X-1)-(X-15), it connects with L <^{1> in the} site | part shown by *.

L <^1> in general formula (A) represents a single bond or a bivalent coupling group. As the divalent linking group when L ¹ represents a divalent linking group, a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, methylene group, ethylene group, trimethylene group, propylene group, butyl) Ethylene groups), substituted or unsubstituted arylene groups having 6 to 30 carbon atoms (e.g., phenylene groups, naphthalene groups, etc.), substituted or unsubstituted heterocyclic linking groups, -CH = CH-, -O-, -S -, -NR-, -C (= O)-, -SO-, -SO _2- , a linking group represented by the following general formula (2), a linking group represented by the following general formula (3), or the following general formula ( 4) and a linking group formed by connecting two or more thereof (for example, -N (R) C (= O)-, -OC (= O)-, -C (= O)) N (R)-, -C (= O) O-, wherein R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group]. The divalent linking group in General Formula (A) is not limited to any extent as long as it can exhibit the effects of the present invention.

[In the general formulas (2) to (4), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a hydrogen atom or a substituent. k represents the integer of 0-4. When k is 2 or more, R ³ may be the same or different. In general formulas (2) to (4), * represents a position to bond with the X ¹ group in the formula (A), and ＊＊ represents a position to bind to Dye in the formula (A).]

Dye in general formula (A) represents the pigment | dye residue remove | excluding one arbitrary hydrogen atom from the said general formula (M).

Although the specific example of the structural unit represented by general formula (A) below is shown, this invention is not limited to this.

<Structural Unit Represented by Formula (B)>

Next, the structural unit represented by general formula (B) is demonstrated in detail.

In general formula (B), X <^2> represents the coupling group formed by superposition | polymerization, L <^2> represents a single bond or a bivalent coupling group, A represents the group which can be ion-bonded or coordinate-bonded with Dye, and Dye is said general formula (M The dye residue which can ion-bond or coordinate-bond with A by removing one hydrogen atom from () is shown.

Group represented by X <^2> , L <^2> in general formula (B) represents group of the same as X <^1> , L <^{1> in the} said General formula (A), respectively, and its preferable range is also the same.

The group represented by A in General Formula (B) may be a group capable of ionically bonding or coordinating Dye with Dye, and any of anionic groups and cationic groups may be used as the group capable of ionically bonding. The anionic group is preferably an anionic group having a pKa of 12 or less, such as a carboxyl group, a phospho group, a sulfo group, an acylsulfonamide group, and a sulfonimide group, more preferably pKa is 7 or less, and still more preferably 5 or less.

Although the specific example preferable as anionic group is shown below, this invention is not limited to these. In the anionic group shown below, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

As a cationic group represented by A in General formula (B), a substituted or unsubstituted onium cation (for example, a substituted or unsubstituted ammonium group, a pyridinium group, an imidazolium group, a sulfonium group, a phosphonium group, etc.) is preferable. Especially, a substituted ammonium group is preferable.

Although the specific example preferable as a cationic group is shown below, this invention is not limited to these. In addition, in the cationic group shown below, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Although the specific example of the structural unit represented by general formula (B) is shown below, this invention is not limited to this.

<Structural unit represented by general formula (C)>

Next, the structural unit represented by general formula (C) is demonstrated in detail.

In general formula (C), L <^3> represents a single bond or a bivalent coupling group, and when two or more L <^3> exists, the structure of L <^3> may be same or different. Dye represents the pigment | dye residue remove | excluding two arbitrary hydrogen atoms from the said General formula (M). n3 represents the integer of 1-4.

As a bivalent coupling group represented by L <^3> in the said General formula (C), a C1-C30 substituted or unsubstituted linear, branched or cyclic alkylene group (for example, methylene group, ethylene group, trimethylene group, propylene group) , Butylene group), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, —S—, —NR—, —C (═O) —, —SO—, —SO ₂ —, and a linking group formed by linking two or more thereof (eg, —N (R) C (═O) -, -OC (= O)-, -C (= O) N (R)-, -C (= O) O-, -N (R) C (= O) N (R)-, etc.) are preferable. It can be heard. Herein, each of R in the above formulas independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Although the specific example used preferably as a bivalent coupling group represented by L <^3> in general formula (C) is described below, it is not limited to these as L <^3> of this invention.

Although the specific example of the structural unit represented by general formula (C) is shown below, this invention is not limited to this.

<Copolymerization Component>

Although the dye multimer in this invention may be formed only from the structural unit represented by the said general formula (A), general formula (B), or general formula (C), it may be multiplied with another structural unit. As another structural unit, Preferably it is a structural unit shown below, Although these specific examples are shown, this invention is not limited to these.

<Dye multimer represented by general formula (D)>

Next, the dye multimer represented by General formula (D) is explained in full detail.

In General Formula (D), L ⁴ represents an n4-valent linking group, n ⁴ represents an integer of 2 to 100, and a plurality of Dyes each independently represent a dye residue obtained by removing one arbitrary hydrogen atom from General Formula (M). Indicates.

N4 in the said general formula (D) becomes like this. Preferably it is 2-80, More preferably, it is 2-40, Especially preferably, it is 2-10.

In the formula (D), if n4 is 2 as the divalent connecting group represented by L ^4, for a straight-chain, branched or cyclic alkylene group (such as a substituted or unsubstituted 1 to 30 carbon atoms, a methylene group, an ethylene group, Trimethylene group, propylene group, butylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, -CH = CH —, —O—, —S—, —NR—, —C (═O) —, —SO—, —SO ₂ —, and a linking group formed by linking two or more thereof [eg, —N (R ) C (= O)-, -OC (= O)-, -C (= O) N (R)-, -C (= O) O-, -N (R) C (= O) N (R ), Etc.] are mentioned preferably. Herein, each of R in the above formulas independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Examples of the n4-valent linking group where n 4 is 3 or more include a substituted or unsubstituted arylene group (1,3,5-phenylene group, 1,2,4-phenylene group, 1,4,5,8-naphthalene group, etc.), heterocyclic linking group (Eg, a 1,3,5-triazine group, etc.), an alkylene linking group, etc. are made into a central mother nucleus, and the linking group formed by substitution of the said bivalent linking group is mentioned.

Although the specific example of the dye multimer represented by general formula (D) below is shown, this invention is not limited to this.

Below, the example preferable as a dye multimer in this invention is shown in following Table 1 including the structural unit (the said structural unit), copolymerization mass ratio, a weight average molecular weight, and dispersion degree.

Although it is preferable that the dye multimer in this invention contains the structural unit represented by the said general formula (A), general formula (B), or general formula (C) as a part as a general formula (A) among these, It is preferable to include the structural unit represented by.

The dye multimer in this invention contains 100 mass% of structural units represented by the said General formula (A), General formula (B), or General formula (C) by mass ratio (mass%), ie, the said The multimer obtained by superposing | polymerizing only the structural unit represented by general formula (A), general formula (B), or general formula (C) may be sufficient.

It is preferable to contain 10 mass%-100 mass% of structural units represented by general formula (A), general formula (B), or general formula (C) in mass ratio (mass%) in a dye multimer from a viewpoint of coloring power. It is more preferable to contain 20 mass%-100 mass%, and it is still more preferable to contain 30 mass%-100 mass%.

The synthesis | combining method of the dye multimer in this invention is demonstrated using the above-mentioned S-4 as an example.

Synthesis of Example Compound S-4

23 g (0.034 mol) of commercial xanthene dyes (Acid Red 289: Tokyo Kasei Hing) were added to sulfolane (150 ml), and 40 g (0.34 mol) of chlorosulfonic acid was added dropwise while stirring at 5 ° C. This solution was heated until it became 80 degreeC of internal temperature, and it stirred for 4 hours in that temperature state. After the reaction liquid temperature was lowered to about 30 ° C., thionyl chloride 40 g (0.34 mol) was slowly added dropwise, and the mixture was further heated to 80 ° C. and stirred for 4 hours. The reaction solution was poured into ice water, and the precipitated acid chloride was filtered off and dried.

Separately, 2-aminoethanol (1.2 g, 0.02 mol) dissolved in acetonitrile was cooled to an internal temperature of 5 ° C., and the first obtained acid chloride was slowly added. The reaction solution temperature was raised to 40 ° C, stirred for 4 hours, poured into ice water, and the precipitated crystals were separated by filtration and dried to obtain an alcohol (5.7 g, 0.008 mol).

After dissolving the alcohol in N, N-dimethylacetamide (50 ml), methacrylic acid chloride was added at 5 ° C and stirred for 3 hours as it was. The reaction solution was poured into water, and the precipitated crystals were separated by filtration and dried to obtain a Q-1 body (4.7 g, 0.0072 mol).

The obtained Q-1 (4 g), methacrylic acid (0.54 g) and dodecanethiol (0.1 g) were dissolved in 10.0 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and then stirred at 85 ° C. with dimethyl 2 The solution which melt | dissolved 2'- azobis (2-methylpropionate) (0.2 g) in 1 g of PGMEA was dripped over 3 hours. 4 hours after the start of dropwise addition, dimethyl 2,2'-azobis (2-methylpropionate) (0.2 g) was added, and stirring was continued at 85 ° C for 2 hours. 200 ml of PGMEA and 200 ml of methanol were added to the reaction solution, and this was added dropwise while stirring with ice water. Precipitated crystals were filtered off, and the obtained crystals were dried under reduced pressure to obtain 3.9 g of Exemplary Compound S-4.

As for the structure of S-4, the disappearance of the peak of 5.56-6.12 corresponding to the polymerizable group moiety of Q-1 was confirmed by ¹ H-NMR, and the introduction of methacrylic acid was confirmed by acid value measurement.

It is preferable that the molecular weight of the dye multimer in this invention is the range of 3000-20000 in the range of 5000-30000 and the number average molecular weight (Mn) by a weight average molecular weight (Mw). More preferably, it is the range of 5000-25000 in weight average molecular weight (Mw), and the range of 3000-17000 in number average molecular weight (Mn). Especially preferably, it is the range of 5000-20000 in weight average molecular weight (Mw), and the range of 3000-15000 in number average molecular weight (Mn).

It is preferable that the weight average molecular weight (Mw) of a specific polymer is 20000 or less from a developable viewpoint at the time of applying the dye multimer in this invention to a colored curable composition, and producing a color filter.

≪Coloring curable composition≫

The colored curable composition of this invention contains at least 1 type of said dye multimer in this invention as a coloring agent, and also contains (b) polymeric compound, (c) photoinitiator, and (d) organic solvent. The colored curable composition of this invention is hardened | cured by heat, light, or both, It can be comprised using other components, such as a binder and a crosslinking agent, as needed.

By the characteristic of the compound which has a xanthene skeleton as a partial structure of a pigment | dye site | part, the colored curable composition of this invention can form a pixel pattern in thin film (for example, 1 micrometer or less in thickness). Accordingly, the colored curable composition of the present invention is required to have a high definition of 2 micrometers or less of a small size (a variation of the pixel pattern viewed from the substrate normal direction, for example, 0.5 to 2.0 mu m), and a good rectangular cross-sectional profile. It is especially preferable for manufacture of the color filter for solid-state image sensors.

In the colored curable composition of this invention, the said dye multimer may be used individually by 1 type, and may be used together 2 or more types.

Although content of the said dye multimer in the colored curable composition of this invention changes with the molecular weight and molar extinction coefficient of the said dye multimer, 10 mass%-70 mass% are preferable with respect to the total solid component of a colored curable composition, 10 mass%-50 mass% are more preferable, and 15 mass%-30 mass% are the most preferable.

Coloring agents other than the said dye multimer can also be used for the colored curable composition of this invention and the color filter using the said colored curable composition in the range which does not impair the effect of this invention. For example, triarylmethane-based colorants having an absorption maximum at 550 nm to 650 nm (e.g., CI acid blue 7, CI acid blue 83, CI acid blue 90, CI solvent blue 38, CI acid violet 17, CI acid) Violet 49, CI acid green 3, etc.), the xanthene pigment | dye which has an absorption maximum in 500 nm-600 nm, for example, CI Acid red 289 and the like can be used.

The content of the triaryl methane-based coloring agent may be in a range which does not impair the effects of the present invention, and is preferably 0.5% by mass to 50% by mass based on the total solid of the colored curable composition of the present invention.

Moreover, in order to produce a blue filter array, it is preferable to mix and use at least 1 sort (s) and a phthalocyanine-type pigment for the said dye multimer.

Phthalocyanine Pigment

The phthalocyanine-based pigment that can be used in the present invention is not particularly limited as long as it is a pigment having a phthalocyanine skeleton. In addition, as a center metal contained in a phthalocyanine type pigment, what is necessary is just a metal which can comprise a phthalocyanine skeleton, and it is not specifically limited. Among them, magnesium, titanium, iron, cobalt, nickel, copper, zinc and aluminum are preferably used as the center metal.

Specifically, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 1, C.I. Pigment Blue 15: 2, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 5, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 16, C.I. Pigment Blue 17: 1, C.I. Pigment Blue 75, C.I. Pigment Blue 79, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment green 37, chloro aluminum phthalocyanine, hydroxy aluminum phthalocyanine, aluminum phthalocyanine oxide, and zinc phthalocyanine. Among them, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 6, Pigment Blue 15: 1, C.I. Pigment Blue 15: 2 is preferred, in particular C.I. Pigment Blue 15: 6 is preferred.

As for content in the colored curable composition of the phthalocyanine-type pigment in this invention, 10 mass%-70 mass% are preferable with respect to the total solid component of a colored curable composition, 20 mass%-60 mass% are more preferable, 35 The mass%-50 mass% are the most preferable.

In addition, the content ratio of the dye multimer which has the said xanthene skeleton as a partial structure of a pigment | dye site | part, and the phthalocyanine type pigment is represented by the ratio of the dye multimer which has a xanthene skeleton as a partial structure of a pigment | dye part, and is a phthalocyanine pigment: pigment multimer = 100: 5-100: 100 are preferable, 100: 15-100: 75 are more preferable, and 100: 25-100: 50 are still more preferable.

(Dispersant)

The colored curable composition of the present invention may contain a dispersant when it contains a pigment.

As the pigment dispersant which can be used in the present invention, a polymer dispersant [for example, polyamideamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylic Latex, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like.

Polymeric dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from the structure.

The polymeric dispersant adsorbs on the surface of the pigment and acts to prevent reagglomeration. Therefore, the terminal modified | denatured type | mold polymer | macromolecule, a graft type polymer, and a block type polymer which have an anchor site to a pigment surface are mentioned as a preferable structure.

On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

As a terminal modified type polymer which has an anchor site | part to a pigment surface, For example, the polymer which has a phosphoric acid group in the terminal described in Unexamined-Japanese-Patent No. 3-112992, 2003-533455, etc., Unexamined-Japanese-Patent No. 2002-273191 The polymer which has a sulfonic acid group at the terminal described in Unexamined-Japanese-Patent etc., the polymer which has the partial skeleton and heterocycle of the organic pigment of Unexamined-Japanese-Patent No. 9-77994, etc. are mentioned. Moreover, the polymer which introduce | transduced the anchor site (acidic group, basic group, partial skeleton of organic pigment, heterocyclic ring, etc.) to two or more pigment surfaces in the polymer terminal of Unexamined-Japanese-Patent No. 2007-277514 also has excellent dispersion stability, desirable.

As the graft polymer having an anchor portion on the pigment surface, for example, poly (lower alkylene) described in Japanese Patent Application Laid-Open No. 54-37082, Japanese Patent Application Laid-Open No. 8-507960, Japanese Patent Application Laid-Open No. 2009-258668, and the like. Imine) and polyester, the reaction product of polyallylamine and polyester described in Japanese Patent Application Laid-open No. Hei 9-169821, etc., and the macromolecule described in Japanese Patent Application Laid-open No. Hei 10-339949, Japanese Patent Laid-Open No. 2004-37986 Graft-type polymers having partial skeletons and heterocycles of organic pigments described in copolymers of monomers and nitrogen atom monomers, JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc. And copolymers of macromonomers and acid group-containing monomers described in JP-A 2010-106268 and the like. In particular, the amphoteric dispersing resin having a basic group and an acidic group described in JP-A-2009-203462 is particularly preferable in view of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the colored curable composition using the pigment dispersion.

As a macromonomer used when producing a graft-type polymer which has an anchor site to a pigment surface by radical polymerization, a well-known macromonomer can be used and macromonomer AA-6 by Toagosei Co., Ltd. (terminal group is methacryl) Dimethylmethyl methacrylate, AS-6 (polystyrene whose terminal group is methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile whose terminal group is methacryloyl group), AB-6 (terminal group Butyl polyacrylate which is a methacryloyl group), Flaccel FM5 ((epsilon) 5 molar equivalent addition product of 2-hydroxyethyl methacrylate) made by Daicel Kagaku Kogyo Co., Ltd., FA10L (2-hydroxy acrylate) 10 mol equivalents of (epsilon) -caprolactone adduct of oxyethyl), the polyester-type macromonomer of Unexamined-Japanese-Patent No. 2-272009, etc. are mentioned. Among them, a polyester macromonomer having excellent flexibility and affinity for solvents is particularly preferable in view of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the colored curable composition using the pigment dispersion. Most preferred are polyester-based macromonomers such as polyester-based macromonomers described in -272009.

As a block type polymer which has an anchor part to a pigment surface, the block type polymer of Unexamined-Japanese-Patent No. 2003-49110, Unexamined-Japanese-Patent No. 2009-52010, etc. are preferable.

The pigment dispersant which can be used for this invention can also be obtained as a commercial item, As such a specific example, "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 made by BYK Chemie. (Polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA4047, 4050-4165 by EFKA company " (Polyurethane), EFKA4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 ( Phthalocyanine derivative), 6750 (azo pigment derivative), "Azisper PB821, PB822, PB880, PB881" made by Ajinomoto Fine Techno Co., Ltd., "Florene TG-710 (urethane oligomer)" by Kyoeisha Chemical Co., Ltd., "Polyester Flow No.50E, No.300 (Acrylic Copolymer), Kusumoto Kasei "Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyhydric carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725", "demolable" RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), "homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920, 930, 935 , 985 (polyoxyethylene nonylphenyl ether), "acetamine 86 (stearylamine acetate)", "Solpers 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine) by Nippon Lubrizol company ), 3000, 17000, 27000 (polymer having functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer), Nikko T106 (polyoxyethylene sorbitan monooleate), MYS-IEX made by Nikko Chemical (Polyoxyethylene monostearate), Kawaken Fine Chemical Co., Ltd. Hinoact T-8000E, Ionnet S-20 made by Sanyo Kasei Co., Ltd. Can be mentioned.

These pigment dispersants may be used independently and may be used in combination of 2 or more type. In this invention, it is especially preferable to use a combination of a pigment derivative and a polymer dispersing agent.

As the pigment dispersant of the present invention, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor portion on the pigment surface may be used in combination with an alkali-soluble resin. As alkali-soluble resin, it has a (meth) acrylic acid copolymer, itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, etc., and an acidic cellulose derivative which has a carboxylic acid group in a side chain, and a hydroxyl group. Although the resin which modified | denatured the polymer by the acid anhydride is mentioned, A (meth) acrylic acid copolymer is especially preferable. Moreover, the N-position substituted maleimide monomer copolymer of Unexamined-Japanese-Patent No. 10-300922, the ether dimer copolymer of Unexamined-Japanese-Patent No. 2004-300204, and the polymeric group of Unexamined-Japanese-Patent No. 7-319161. Alkali-soluble resins containing are also preferable.

As content of the pigment dispersing agent in a polymeric composition, it is preferable that it is 1-80 mass parts with respect to 100 mass parts of pigments which are coloring agents, 5-70 mass parts is more preferable, It is further more preferable that it is 10-60 mass parts.

Specifically, in the case of using a polymer dispersant, the amount thereof is preferably in the range of 5 to 100 parts, more preferably in the range of 10 to 80 parts, in terms of mass with respect to 100 parts by mass of the pigment.

Moreover, when using a pigment derivative together, it is preferable that it is in the range of 1-30 parts in mass conversion with respect to 100 mass parts of pigments as a usage-amount of a pigment derivative, It is more preferable to exist in the range of 3-20 parts, The range of 5-15 parts It is particularly preferred to be at.

In the polymerizable composition, when a pigment is used as a coloring agent and a pigment dispersant is further used, the total content of the coloring agent and the dispersant is 30% by mass or more based on the total solids constituting the polymerizable composition in terms of curing sensitivity and color concentration. It is preferable that it is mass% or less, It is more preferable that they are 40 mass% or more and 85 mass% or less, It is still more preferable that they are 50 mass% or more and 80 mass% or less.

<(b) polymeric compound>

The colored curable composition of this invention can be comprised preferably by containing at least 1 sort (s) of (b) polymeric compound. The polymerizable compound is mainly included when the colored curable composition is constituted in a negative form.

In addition, a polymeric compound can be contained with the photoinitiator mentioned later in the positive type containing a naphthoquinone diazide compound, In this case, the hardening degree of the pattern formed can be promoted more. Hereinafter, a polymeric compound is demonstrated.

Specifically as said polymeric compound, it is selected from the compound which has at least 1, preferably 2 or more terminal ethylenically unsaturated bond. Such compound groups are widely known in the above industrial field, and in the present invention, these can be used without particular limitation. These may be, for example, any of chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and (co) polymers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

Examples of the monomer and its (co) polymer include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and these ( And co-polymers. Preferably, they are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and (co) polymers thereof. Moreover, the addition reaction product of the monofunctional or polyfunctional isocyanate or epoxy of unsaturated carboxylic ester or amides which have nucleophilic substituents, such as a hydroxyl group, an amino group, and a mercapto group, or a monofunctional or polyfunctional carboxyl Acid dehydration condensation reactants are also preferably used. Moreover, the addition reaction product of unsaturated carboxylic acid ester or amides which have electrophilic substituents, such as an isocyanate group and an epoxy group, and monofunctional or polyfunctional alcohols, amines, and thiols, and also detachable substituents, such as a halogen group and a tosyloxy group Substituted reactants of unsaturated carboxylic acid esters or amides having monofunctional or polyfunctional alcohols, amines and thiols are also preferable. As another example, it is also possible to use a compound group in which the unsaturated carboxylic acid is substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like.

As these specific compounds, Paragraph No. 0095-Paragraph No. 0108 of Unexamined-Japanese-Patent No. 2009-288705 can also be used suitably also in this invention.

Moreover, as said polymeric compound, the compound which has an ethylenically unsaturated group which has a boiling point of 100 degreeC or more under the normal pressure which has at least 1 addition-polymerizable ethylene group as a polymerizable monomer is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, trimethol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocy (Meth) acrylated after addition of ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin or trimetholethane, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034 , Urethane acrylates described in Japanese Patent Laid-Open No. 51-37193, Japanese Patent Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, Il Polyfunctional acrylates, methacrylates, and mixtures thereof, such as the polyester acrylates described in each patent publication No. 52-30490, epoxy acrylate which is a reaction product of an epoxy resin, and (meth) acrylic acid, are mentioned. Can be.

Moreover, as a compound which has a boiling point of 100 degreeC or more under normal pressure, and has an ethylenically unsaturated group which can be at least 1 addition polymerization, the compound of Paragraph No. [0254]-[0257] of Unexamined-Japanese-Patent No. 2008-292970 is also preferable.

In addition to the above, radically polymerizable monomers represented by the following General Formulas (MO-1) to (MO-5) can also be preferably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In said general formula, n is 0-14, m is 1-8. Two or more R and T in one molecule may be same or different, respectively.

In each of the radically polymerizable monomers represented by General Formulas (MO-1) to (MO-5), at least one of the plurality of R's is -OC (= 0) CH = CH ₂ , or -OC (= O) C (CH ₃₎ represents a group represented by = CH _2.

As a specific example of the radically polymerizable monomer represented by said general formula (MO-1)-(MO-5), Paragraph No. 0248-Paragraph No. 0251 of Unexamined-Japanese-Patent No. 2007-269779 also apply to this invention. It can be used preferably.

Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a polymerizable monomer.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, but examples thereof include trimetholethane, ditrimethyrolethane, trimetholpropane, ditrimetholpropane, Ε-caprolactone-modified polyfunctional (meth) obtained by esterifying polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimetholmelamine and (meth) acrylic acid and ε-caprolactone Acrylate is mentioned. Especially, the polyfunctional monomer which has a caprolactone structure represented by following formula (i) is preferable.

(6 R of Formula (i) is group represented by following formula (ii), or 1-5 of 6 R is group represented by following formula (ii), and remainder is following formula (iii) Is represented by)

(In formula (ii), R ¹ represents a hydrogen atom or a methyl group, m represents the number of 1 or 2, and "*" represents a bond.)

(In formula (iii), R <^1> represents a hydrogen atom or a methyl group, and "*" represents a bond.)

The polyfunctional monomer which has such a caprolactone structure is marketed as KAYARAD DPCA series by Nippon Kayaku Co., Ltd., for example, and DPCA-20 (m = 1, Formula (i) in said Formula (i)-(iii)). ii) the number of groups represented by = 2 and R ¹ are all hydrogen atoms), DPCA-30 (formula, m = 1, the number of groups represented by formula (ii) = 3, R ¹ are all hydrogen) A compound which is an atom), DPCA-60 (the formula, m = 1, the number of groups represented by formula (ii) = 6, R ¹ are all hydrogen atoms), DPCA-120 (m = 2 in the formula) , The number of groups represented by formula (ii) = 6, and R ¹ are all hydrogen atoms).

In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

As for content of the polymeric compound in the colored curable composition of this invention, 0.1 mass%-90 mass% are preferable with respect to solid content in a colored curable composition, 1.0 mass%-80 mass% are more preferable, 2.0 mass%-70 Mass% is particularly preferred.

In the colored curable composition of this invention, the content mass ratio (dye multimer: polymeric compound in this invention) of the dye multimer in this invention and a polymeric compound is 1: 2-20: 1 from a thinning viewpoint. It is preferable that it is 1: 1, and it is more preferable that it is 1: 1-10: 1.

<(c) Photoinitiator>

The colored curable composition of this invention contains the (c) photoinitiator.

The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound described above, and is preferably selected from the viewpoints of properties, start efficiency, absorption wavelength, availability, cost, and the like.

As a photoinitiator, For example, the at least 1 active halogen compound chosen from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl substituted coumarin compound, a lophine dimer, a benzophenone compound, an acetophenone compound And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds. As a specific example of a photoinitiator, the thing of Paragraph 0070-0077 of Unexamined-Japanese-Patent No. 2004-295116 is mentioned. Especially, an oxime type compound is preferable from a point with which a polymerization reaction is rapid.

There is no restriction | limiting in particular as said oxime type compound (henceforth an "oxime type photoinitiator"), For example, it is described in Unexamined-Japanese-Patent No. 2000-80068, WO02 / 100903A1, Unexamined-Japanese-Patent No. 2001-233842, etc. An oxime type compound is mentioned.

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

Among them, 2- (o-benzoyl oxime) -1- [4- (phenylthio) phenyl] -1 in that a good pattern of a shape (particularly, a rectangular shape of a pattern in the case of a solid-state imaging device) can be obtained with a smaller exposure dose Oxime-o-acyl systems, such as 2, 2-octanedione and 1- (o-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone A compound is especially preferable, Specifically, OXE-01, OXE-02 (above, BASF Corporation), etc. are mentioned, for example.

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

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

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

As A, since the sensitivity is improved and the coloring by time of heating is suppressed, the alkylene group substituted by unsubstituted alkylene group and alkyl group (for example, methyl group, ethyl group, tert- butyl group, and dodecyl group), alkenyl group (for example, For example, an alkylene group substituted with a vinyl group, an allyl group, an aryl group (for example, a phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) The alkylene group substituted with is preferable.

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

X may be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent in view of solvent solubility and the absorption efficiency improvement of a long wavelength region. The alkoxy group, the aryloxy group which may have a substituent, the alkylthioxy group which may have a substituent, the arylthioxy group which may have a substituent, and the amino group which may have a substituent are preferable.

In addition, n in formula (E) and (F) has preferable integer of 1-2.

Hereinafter, although the specific example of a compound represented by Formula (E) and (F) is shown below, this invention is not limited to these.

Moreover, you may use other well-known photoinitiator of Paragraph 0079 of Unexamined-Japanese-Patent No. 2004-295116 for the coloring curable composition of this invention other than the said photoinitiator.

A photoinitiator can be contained individually by 1 type or in combination of 2 or more types.

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

<(d) organic solvent>

The colored curable composition of this invention contains the (d) organic solvent.

The organic solvent is not particularly limited as long as it can satisfy the solubility of each component to coexist and the coating property when the colored curable composition is used, and in particular, the organic solvent is preferably selected in consideration of the solubility, the coatability, and the safety of the binder. .

As the organic solvent, for example, ethyl acetate, acetic acid-n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate Ethyl lactate, oxyacetic acid alkyl esters (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically methyl methoxyacetate, methoxyacetic acid ethyl, methoxyacetic butyl, ethoxyacetic acid methyl, ethoxyacetic acid) Ethyl, etc.), 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, and the like (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3) Methyl ethoxypropionate, ethyl 3-ethoxypropionate, and the like)) and 2-oxypropionic acid alkyl esters ( Examples: methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate (specifically methyl 2-methoxypropionate, ethyl 2-methoxypropionic acid, 2-methoxypropionic acid propyl, 2-ethoxypropionic acid Methyl, ethyl 2-ethoxypropionate, and the like)), methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate (specifically methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. are mentioned. Can be.

As the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.

As ketones, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. are mentioned, for example.

As aromatic hydrocarbons, toluene, xylene, etc. are mentioned preferably, for example.

When these organic solvents contain the solubility of each component mentioned above, and an alkali-soluble binder, it is also preferable to mix 2 or more types from a viewpoint of the solubility, improvement of a coated surface shape, etc. In this case, particularly preferably methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, It is a mixed solution comprised from 2 or more types chosen from cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

As content in the colored curable composition of the organic solvent, the quantity which becomes 10 mass%-80 mass% of the total solid content concentration in a composition is preferable, and the quantity which becomes 15 mass%-60 mass% is more preferable.

(Other ingredients)

In addition to each component mentioned above, the coloring curable composition of this invention may further contain other components, such as an alkali-soluble binder and a crosslinking agent, in the range which does not impair the effect of this invention.

Alkali-soluble binder

An alkali-soluble binder is not specifically limited except having alkali solubility, Preferably it can select from a viewpoint of heat resistance, developability, water availability, etc ..

The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and capable of being developed with a weak alkaline aqueous solution. As such linear organic polymer, a polymer having a carboxylic acid in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid described in each of the publications of 54-25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048 Copolymers, partially esterified maleic acid copolymers, and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are likewise useful. Moreover, the polymer (for example, the compound of Unexamined-Japanese-Patent No. 2004-300203) formed by superposing | polymerizing the compound of the specific structure which is an ether dimer of 2- (hydroxyalkyl) acrylic acid ester is also useful.

As another preferable example of the binder in this invention, the polymer containing the structural unit derived from the compound represented by the following general formula (ED) (henceforth "ether dimer" suitably) as a polymerization component is mentioned.

In said general formula (ED), R <^21> and R <^22> represents a C1-C25 hydrocarbon group which may respectively independently have a hydrogen atom or a substituent.

By using the binder containing the structural unit derived from an ether dimer, the polymeric composition of this invention has the advantage that the cured coating film which was extremely excellent also in transparency with heat resistance can be formed.

Although there is no restriction | limiting in particular as a C1-C25 hydrocarbon group which may have a substituent represented by R <^21> and R <^22> in the said general formula (ED) which shows the said ether dimer, For example, methyl, ethyl, n-propyl, Linear or branched alkyl groups such as isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl and 2-ethylhexyl; Aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; Alkyl group substituted by alkoxy, such as 1-methoxyethyl and 1-ethoxyethyl; Alkyl groups substituted with aryl groups such as benzyl; Etc. can be mentioned. Among these, substituents of primary or secondary carbon, which are difficult to be detached by an acid or heat such as methyl, ethyl, cyclohexyl, benzyl and the like, are preferable in terms of heat resistance.

As a specific example of the said ether dimer, for example, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2 -Propenoate, di (n-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] Bis-2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis ( Methylene)] bis-2-propenoate, di (t-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'- [Oxybis (methylene)] bis-2-propenoate, di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1-meth Methoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate , Di (1-ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-prop Phenoate, diphenyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2-propenoate, Di (t-butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] Bis-2-propenoate, di (tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxy Bis (methylene)] bis-2-propenoate, diamantyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl)- 2,2 '-[oxybis (methylene)] bis-2-propenoate, etc. are mentioned.

Among them, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate and dicyclo Hexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate are preferable. 1 type of structural units derived from these ether dimers may be contained in a binder, and may be contained 2 or more types.

The binder containing the structural unit derived from the compound represented by the said general formula (ED) may be a copolymer containing the structural unit derived from the monomer other than the structural unit derived from the compound represented by the general formula (ED). Although it does not specifically limit as another monomer which can be used together, For example, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, As vinyl compounds, such as cyclohexyl (meth) acrylate, styrene, (alpha) -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate , N-phenylmaleimide and N- as N-substituted maleimide monomers described in Japanese Patent Application Laid-Open No. 10-300922, such as polystyrene macromonomer and polymethyl methacrylate macromonomer. Claw-hexyl maleimide imide, etc. may be mentioned, are appropriately used in combination within a range not to impair the properties of the ether dimer.

In addition to the above, the alkali-soluble binder in the present invention includes an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, and a poly (2-hydroxyethyl (meth) acrylate. ), Polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful. In addition, the linear organic polymer may be a copolymer of a monomer having hydrophilicity. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-metholacrylamide, secondary or tertiary alkylacrylamide, di Alkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) Acrylate, a branched or linear propyl (meth) acrylate, a branched or linear butyl (meth) acrylate, or phenoxyhydroxypropyl (meth) acrylate etc. are mentioned. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphate ester group, quaternary ammonium base group, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and the group derived from salt thereof, and morpholine ethyl group. Monomers are also useful.

Moreover, an alkali-soluble binder may have a polymeric group in a side chain in order to improve crosslinking efficiency, For example, the polymer etc. which contain an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in a side chain are also useful. As an example of the polymer containing the above-mentioned polymerizable group, Diamond NR series (made by Mitsubishi Rayon Co., Ltd.), Photomer6173 (COOH containing polyurethane acrylic oligomer. (All made by Osaka Yuki Kagaku Kogyo KK), the Pycloma P series, the Plascel CF200 series (all made by Daicel Kagaku Kogyo KKK), Ebecryl 3800 (made by Daicel Yushibi KK) Can be. Moreover, alcohol soluble nylon, the polyether of 2, 2-bis- (4-hydroxyphenyl) propane, and epichlorohydrin etc. are also useful in order to raise the intensity | strength of a hardened film.

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

As said acrylic resin, the copolymer which consists of a monomer chosen from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, etc., the said photomer 6173, KS resist-106, Cychroma P series and the like are preferable.

The alkali-soluble binders as the developing property, the weight-average molecular weight in terms of solution viscosity (a polystyrene conversion value measured by GPC method) of the polymer is preferably 1000~2 × 10 ^5, more preferably the polymer 2000~1 × 10 ⁵ And, the polymer of 5000-5 * 10 <^4> is especially preferable.

-Cross-linking system-

The hardness of the colored cured film formed by hardening | curing a colored curable composition using a crosslinking agent supplementally to the colored curable composition of this invention can also be made higher.

The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. Examples of the crosslinking agent include at least one substituent selected from (a) epoxy resins, (b) methrol groups, alkoxymethyl groups, and acyloxymethyl groups. Phenol compound, naphthol compound or hydroxyanthracene substituted with at least one substituent selected from melamine compound, guanamine compound, glycoluril compound or urea compound, (c) metholol group, alkoxymethyl group, and acyloxymethyl group The compound can be mentioned. Especially, polyfunctional epoxy resin is preferable.

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

Polymerization inhibitor

In the colored curable composition of this invention, it is preferable to add a small amount of polymerization inhibitors in order to prevent unnecessary thermal polymerization of a polymeric compound during manufacture or storage of the said colored curable composition.

Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3 -Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine 1st cerium salt, etc. are mentioned.

As for the addition amount of a polymerization inhibitor, about 0.01 mass%-about 5 mass% are preferable with respect to the mass of the whole composition.

-Surfactants-

You may add surfactant to the colored curable composition of this invention. As surfactant, various surfactants, such as a fluorine-type surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone type surfactant, can be used.

In particular, by containing a fluorine-based surfactant, the liquid characteristics (particularly fluidity) when the coating liquid is used can be further improved, and the uniformity and liquid saving property of the coating thickness can be further improved.

That is, in the polymeric composition containing a fluorine-type surfactant, the wettability to a to-be-coated surface is improved by reducing the interfacial tension of a to-be-coated surface and a coating liquid, and the coating property to a to-be-coated surface improves. For this reason, even when a thin film of several micrometers to several tens of micrometers is formed with a small amount of liquid, it is effective at the point which can form the film of uniform thickness with a small thickness variation more preferable.

The fluorine content in the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, particularly preferably 7% by mass to 25% by mass. If the fluorine content is within this range, it is effective in terms of coating thickness uniformity and liquid saving property, and the solubility in the composition is also good.

As a fluorine type surfactant, Megapack F171, copper F172, copper F173, copper F176, copper F177, copper F141, copper F142, copper F143, copper F144, copper R30, copper F437, copper F475, copper F479, copper F482 , Copper F554, copper F780, copper F781 (above, made by DIC Corporation), fluoride FC430, copper FC431, copper FC171 (or more, manufactured by Sumitomo Rem Co., Ltd.), Supron S-382, copper SC-101 , SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) Can be.

Moreover, as cationic surfactant, a phthalocyanine derivative (commercially available EFKA-745 (made by Morishita Sangyo)), an organosiloxane polymer KP341 (made by Shin-Etsu Kagaku Kogyo Co., Ltd.), (meth) acrylic acid type (co) polymer polyflow No. 75, No. 90, No. 95 (made by Kyueisha Yushi Kagaku Kogyo Co., Ltd.), W001 (made by Yusho Corporation), etc. are mentioned.

Specific examples of the nonionic surfactants include glycerol, trimetholpropane, trimetholethane and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.) and polyoxyethylene. Lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 etc. made by Corporation, and Solsper 20000 (made by Geneca) etc. are mentioned.

Specifically as anionic surfactant, W004, W005, W017 (made by Yusho Corporation), etc. are mentioned.

As silicone type surfactant, Toray Silicone DC3PA, "Copper SH7PA", "Copper DC11PA", "Copper SH21PA", "Copper SH28PA", "Copper SH29PA", "Copper SH30PA", East SH8400 '', Momentive Performance Materials, Inc.``TSF-4440 '', `` TSF-4300 '', `` TSF-4445 '', `` TSF-444 (4) (5) (6) (7) 6 '', `` TSF -4460 "," TSF-4452 "," KP341 "by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "by Big Chemical Co., Ltd., etc. are mentioned.

You may combine two or more types of surfactant.

-Other additives-

Various additives, for example, a filler, an adhesion promoter, an antioxidant, a ultraviolet absorber, an aggregation inhibitor, etc. can be mix | blended with a colored curable composition as needed. As these additives, Paragraph 0155 of Unexamined-Japanese-Patent No. 2004-295116-the thing of 0156 can be mentioned.

In the colored curable composition of this invention, the sensitizer and light stabilizer of Paragraph 0078 of Unexamined-Japanese-Patent No. 2004-295116, and the thermal polymerization inhibitor of Paragraph 0081 of this publication can be contained.

In addition, in order to promote alkali solubility in the non-exposed areas and to improve the developability of the colored curable composition, the addition of an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less, is added to the composition. It is preferable to carry out.

Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sublinic acid, azeline acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and canforonic acid; Aromatic mono carboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamonic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, coumalic acid and umbelic acid. .

[Preparation method of colored curable composition]

The colored curable composition of this invention is prepared by mixing the above-mentioned component.

In addition, in preparation of a colored curable composition, you may mix | blend each component which comprises a colored curable composition, and may mix | blend sequentially after melt | dissolving and disperse | distributing each component to a solvent. In addition, the addition order and working conditions at the time of compounding are not restrict | limited. For example, a composition may be prepared by dissolving and dispersing all the components in a solvent at the same time, and if necessary, each component is suitably set as two or more solutions and dispersions, and when used (mixed), these are mixed and prepared as a composition. You may also

The colored curable composition prepared as mentioned above can be used for use, after filtering-separating using the filter of about 0.01 micrometer-3.0 micrometers of pore diameters, More preferably, about 0.05 micrometer-0.5 micrometers of pore diameters, etc. have.

Since the colored curable composition of this invention is excellent in storage stability and can form the colored cured film excellent in light resistance, the color filter used for a liquid crystal display device (LCD) or a solid-state image sensor (for example, CCD, CMOS, etc.). It can be used suitably for formation of colored pixels, such as printing ink, inkjet ink, and a coating material. In particular, it can use suitably for coloring pixel formation for solid-state image sensors, such as CCD and CMOS.

≪Color filter and its manufacturing method≫

Next, the method (manufacturing method of the color filter of this invention) of manufacturing a color filter using the colored curable composition of this invention is demonstrated.

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

As a support body used for the manufacturing method of the color filter of this invention, an alkali free glass, soda glass, borosilicate glass (pyrex (trademark) glass), quartz glass, and these transparent conductive films which are used for a liquid crystal display element etc. are provided, for example. The photoelectric conversion element board | substrate etc. which are attached, and used for solid-state image sensors, such as CCD and CMOS, etc. are mentioned. These board | substrates may be provided with the black stripe which isolate | separates each pixel. Moreover, you may form a primer layer on these support bodies in order to improve adhesion with an upper layer, to prevent the spread of a substance, or to planarize a surface as needed.

In addition, when rotating coating of a colored curable composition on a support body, in order to reduce the amount of dripping of a liquid, a suitable organic solvent can be dropped and rotated prior to dripping of a colored curable composition, and the fusion of a colored curable composition to a support body can be improved.

In the process of apply | coating the colored curable composition of this invention, even if a colored curable composition adheres to the nozzle of an application | coating device discharge part, the piping part of an application | coating device, the application | coating device, etc., it washes easily using a well-known washing | cleaning liquid, for example. Can be removed. In this case, in order to perform more efficient washing | cleaning removal, it is preferable to use the solvent mentioned above as a washing | cleaning liquid as a solvent contained in the colored curable composition of this invention.

Further, Japanese Patent Laid-Open No. 7-128867, Japanese Patent Laid-Open No. 7-146562, Japanese Patent Laid-Open No. 8-278637, Japanese Patent Laid-Open No. 2000-273370, Japanese Patent Laid-Open No. 2006-85140, The cleaning liquids described in Japanese Patent Application Laid-Open No. 2006-291191, Japanese Patent Application Laid-Open No. 2007-2101, Japanese Patent Application Laid-Open No. 2007-2102, Japanese Patent Application Laid-Open No. 2007-281523, etc., are also used for cleaning removal of the colored curable composition of the present invention. It can use suitably as a washing | cleaning liquid.

It is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether as a washing | cleaning liquid.

These solvents used as washing | cleaning liquid may be used individually, or may mix and use 2 or more types.

When mixing 2 or more types of solvents, the mixed solvent which mixes the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group is preferable. The mass ratio of the solvent having a hydroxyl group and the solvent not having a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 80/20. As a mixed solvent, it is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), It is especially preferable that the ratio is 60/40.

Moreover, in order to improve the permeability of the washing | cleaning liquid with respect to a colored curable composition, you may add surfactant mentioned above as a surfactant which a coloring photosensitive composition can contain.

As conditions for the prebaking, a condition of heating at 70 ° C to 130 ° C for 0.5 to 15 minutes using a hot plate or an oven may be mentioned.

Moreover, although the thickness of the colored curable composition layer formed with a colored curable composition is suitably selected according to the objective, it is generally preferable that it is 0.2 micrometer-5.0 micrometers, It is more preferable that it is 0.3 micrometer-2.5 micrometers, 0.3 micrometer- 1.5 μm is most preferred. In addition, the thickness of the colored curable composition layer here is the film thickness after prebaking.

Subsequently, in the manufacturing method of the color filter of this invention, exposure through a mask is performed to the colored curable composition layer formed on the support body (exposure process).

As light or radiation which can be applied to this exposure, g line | wire, h line | wire, i line | wire, KrF light, and ArF light are preferable, and i line | wire is especially preferable. When using i line | wire as irradiation light, it is preferable to irradiate with the exposure amount of 100mJ / cm <2> -10000mJ / cm <2>.

In addition, the exposed colored curable composition layer can be heated at 70 ° C. to 180 ° C. for about 0.5 to 15 minutes using a hot plate or an oven before the next development treatment.

Moreover, exposure can be performed, flowing nitrogen gas in a chamber in order to suppress the oxidative fading of the coloring agent in a colored curable composition layer.

Subsequently, development is performed with a developing solution with respect to the colored curable composition layer after exposure (development process). This makes it possible to form negative or positive colored patterns (resist patterns).

The developing solution dissolves the uncured portion (non-exposed portion) of the colored curable composition layer and does not dissolve the cured portion (exposed portion), and a combination of various organic solvents, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, and meta Sodium silicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4 Aqueous solutions of organic and inorganic alkaline compounds such as, 0] -7-undecene can be used.

When the developing solution is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 11-13, more preferably pH 11.5-12.5. In particular, an alkaline aqueous solution in which tetraethylammonium hydroxide is adjusted to a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass can be used as a developing solution.

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

The development can be performed by a paddle method, a shower method, a spray method, or the like.

Moreover, after developing using alkaline aqueous solution, it is preferable to wash with water. Although the washing | cleaning system is also suitably selected according to the objective, while a support body is rotated at rotation speeds of 10 rpm-500 rpm, rinse treatment can be performed by supplying pure water from a jet nozzle to a shower image from above the rotation center.

Thereafter, the pattern (resist pattern) formed as necessary may be subjected to post-heating and / or post-exposure to promote curing of the pattern (post-curing step).

UV irradiation process

The ultraviolet irradiation step irradiates ultraviolet light (UV light) with an irradiation light amount [mJ / cm 2] 10 times or more of the exposure amount [mJ / cm 2] in the exposure treatment before development in the pattern after the development treatment in the pattern forming step. . By irradiating UV light to the pattern (coloring curable composition) after image development for a predetermined time between the image development process in a pattern formation process, and heat processing mentioned later, color conversion can be prevented effectively when it heats later, and light resistance improves.

As a light source which irradiates UV light, an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a DEEP UV lamp etc. can be used, for example. Among them, in the ultraviolet light to be irradiated, wavelength light of 275 nm or less can be included, and the light irradiance [mW / cm 2] of the wavelength light of 275 nm or less can be irradiated with 5% or more of the integrated irradiation light intensity of all wavelength light in the ultraviolet light. It is preferable. By setting the irradiation illuminance of wavelength light of 275 nm or less in ultraviolet light to 5% or more, the effect of suppressing color conversion between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively increased. From this point, it is preferable to perform using light sources, such as bright lines, such as i line | wire used for exposure in the said pattern formation process, and other light sources, specifically, a high pressure mercury lamp, a low pressure mercury lamp, etc. Especially, 7% or more is preferable with respect to the integral irradiation intensity of all wavelength light in an ultraviolet light for the same reason as the above. Moreover, 25% or less of the upper limit of the irradiance of the wavelength light of 275 nm or less is preferable.

In addition, the integral illumination illuminance is irradiated light when a curve is obtained by setting the illuminance for each spectral wavelength (emission energy passing through the unit area in unit time; [mW / m 2]) as the vertical axis and plotting the light wavelength [nm] as the horizontal axis. The sum (area) of the illuminance of each wavelength light contained in.

It is preferable to perform irradiation of UV light by the irradiation light quantity [mJ / cm <2>] 10 times or more of the exposure amount at the time of exposure in the said pattern formation process. When the amount of irradiation light in this step is less than 10 times, color conversion between the colored pixels and the upper and lower layers cannot be prevented, and the light resistance may deteriorate.

Especially, 12 times or more and 200 times or less of the exposure amount at the time of exposure in a pattern formation process are preferable, and, as for the irradiation light quantity of UV light, 15 times or more and 100 times or less are more preferable.

In this case, it is preferable that the integral irradiation illuminance in the ultraviolet light to be irradiated is 200 mW / cm 2 or more. When the integral irradiation illuminance is 200 mW / cm 2 or more, the effect of suppressing the color conversion between the colored pixels and the upper and lower layers and the effect of improving the light resistance can be more effectively increased. Especially, 250-2000mW / cm <2> is preferable and 300-1000mW / cm <2> is more preferable.

It is preferable to perform post-heating at 100 degreeC-300 degreeC using a hotplate or oven, More preferably, it is 150 degreeC-250 degreeC. Moreover, 30 second-30000 second are preferable, and, as for a post heating time, More preferably, they are 60 second-1000 second.

On the other hand, post-exposure can be performed by g line | wire, h line | wire, i line | wire, KrF, ArF, UV light, an electron beam, X-ray, etc., but g line | wire, h line | wire, i line | wire, UV light are preferable, and especially UV light This is preferred. When irradiating UV light (UV curing), it is preferable to perform at low temperature of 20 degreeC or more and 50 degrees C or less (preferably 25 degreeC or more and 40 degrees C or less). It is preferable that the wavelength of UV light contains the wavelength of the range of 200 nm-300 nm, As a light source, a high pressure mercury lamp, a low pressure mercury lamp, etc. can be used, for example. The irradiation time is 10 seconds to 180 seconds, preferably 20 seconds to 120 seconds, and more preferably 30 seconds to 60 seconds.

Although either post-exposure and post-heating may be performed first, it is preferable to perform post-exposure before post-heating. This is because by promoting the curing by the post exposure, the deformation of the shape due to the thermal sagging or the lower pulling of the pattern seen in the post heating process is suppressed.

The colored pattern thus obtained constitutes a pixel in the color filter.

In preparation of the color filter which has the pixel of several color, the above-mentioned application | coating process, exposure process, and image development process (hardening process as needed) may be repeated according to desired color number.

Since the color filter (color filter of this invention) obtained by the manufacturing method of the color filter of this invention uses the colored curable composition of this invention, it becomes excellent in light resistance.

Therefore, the color filter of this invention can be used for a solid-state image sensor, such as a liquid crystal display device, a CCD image sensor, a CMOS image sensor, and the camera system using the same, Especially, a coloring pattern is formed into a thin film in a micro size, and It is suitable for the use of the solid-state image sensor which requires a favorable rectangular cross-sectional profile, especially the use of a high-resolution CCD element, CMOS element, etc. exceeding 1 million pixels.

<Solid State Imaging Device>

The solid-state image sensor of this invention is equipped with the color filter of this invention. The color filter of this invention has high light resistance, and the solid-state image sensor provided with this color filter can obtain a good color reproducibility.

As a structure of a solid-state image sensor, if it is a structure which comprises the color filter of this invention and functions as a solid-state image sensor, there is no limitation in particular, For example, the following structures are mentioned.

That is, on the support, it has the transfer electrode which consists of several photodiodes, polysilicon, etc. which comprise the light receiving area of a CCD image sensor (solid-state image sensor), and installs the color filter of this invention on it, and then uses a microlens It is a structure to laminate | stack.

In addition, the camera system provided with the color filter of the present invention includes a cover glass, a micro lens, etc. coated with a camera lens or an IR cut film with a dichroic light from the viewpoint of photobleaching of the color material, and the optical properties of the material are 400 nm or less. It is desirable to absorb some or all of the UV light. The camera system preferably has a structure in which oxygen permeability to the color filter is reduced in order to suppress oxidation fading of the colorant. For example, a part or the whole of the camera system is sealed with nitrogen gas. desirable.

<Liquid crystal display device, organic EL display device>

The color filter of this invention is used for the color filter for liquid crystal display devices, and the organic EL display device. The liquid crystal display device and the organic EL display device provided with the color filter of the present invention can display a high quality image having good color tone of a display image and excellent display characteristics.

For the definition of the display device and the details of each display device, for example, "electronic display device (Aki Sasaki, Ltd., High School Chosaka Co., Ltd., 1990 issued)", "display device (Ibuki Sumaki Aki, Sangyo Tosho Co., Ltd.) Issued in 1989). In addition, about a liquid crystal display device, it describes in the "next-generation liquid crystal display technology (Tatsuo Uchida editorial, 1994, high school chosakai Co., Ltd.)." There is no restriction | limiting in particular in the liquid crystal display device and organic electroluminescent display which can apply this invention, For example, to the liquid crystal display device of the various systems described in said "next-generation liquid crystal display technology", and organic electroluminescent display device. Applicable

You may use the color filter of this invention for the liquid crystal display device of a color TFT system. About the liquid crystal display device of a color | collar TFT system, it describes in the "color TFT liquid crystal display (Kyoritsu Shotan Co., Ltd. 1996 issuance)." In addition, the present invention can be applied to liquid crystal display devices having an enlarged viewing angle such as transverse electric field driving methods such as IPS and pixel division methods such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. .

In addition, the color filter of the present invention can be provided by a bright and high-definition color-filter on array (COA) method. In the COA type liquid crystal display device, in addition to the usual demand characteristics as described above, the demand characteristics for the interlayer insulating film, that is, low dielectric constant and peeling liquid resistance, may be required as the required characteristics for the color filter layer. In the color filter of the present invention, since a dye multimer having excellent color is used, excellent color tone, such as color purity, can provide a COA type liquid crystal display device having high resolution and excellent long-term durability. Moreover, in order to satisfy the required characteristic of low dielectric constant, you may form a resin film on a color filter layer.

These image display methods are described in, for example, page 43 of "EL, PDP, LCD display technology and the latest trends in the market" (Toray Research Center Research and Research Division, 2001).

In addition to the color filter of the present invention, the liquid crystal display device of the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacerr, and a viewing angle compensation film. The color filter of this invention can be applied to the liquid crystal display device comprised from these well-known members. For these members, for example, the market for '94 liquid crystal display peripheral materials and chemicals (Kenta Shima Kentaro Co., Ltd., 1994), and the present situation and future prospects of the 2003 liquid crystal market (the lower volume) (Omote Yoshichichi) Fuji Chimera Kenkyu, 2003).

Backlights are described in SID meeting Digest 1380 (2005) (A.Konno et.al), pages 18 to 24 (Shima Yasuhiro) and pages 25 to 30 (Yagi Takaaki) of the December 2005 issue of the monthly display. .

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

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the acclaim is exceeded. In addition, "part" and "%" are mass references | standards unless there is particular notice.

Example 1-1

(1) Preparation of resist solution A (negative type)

The following components were mixed and dissolved to prepare a resist solution A.

Propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA)... Part 5.20

Cyclohexanone (hereinafter referred to as CyH)... Part 52.60

·bookbinder… 30.50parts

(Methyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer, molar ratio = 60:20:20, average molecular weight 30200 (polystyrene equivalent), 41% cyclohexanone solution)

Dipentaerythritol hexaacrylate... Part 10.20

Polymerization inhibitor (p-methoxyphenol)... 0.006part

Fluorine-based surfactants (DIC Corporation F-475). 0.80part

Photoinitiator: 4-benzoxolane-2,6-bis (trichloromethyl) -s-triazine (TAZ-107 manufactured by Midori Kagaku Co., Ltd.). 0.58part

(2) Preparation of glass substrate with primer layer formed

The glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated baking (200 ° C./20 minutes). Subsequently, the resist solution A obtained in said (1) was apply | coated using the spin coater so that the film thickness after drying might be set to 2 micrometers, and it heat-dried at 220 degreeC for 1 hour, and prepared the glass substrate in which the primer layer was formed. did.

(3) Preparation of colored curable composition

(3-1) C.I. Preparation of Pigment Blue 15: 6 Dispersion

C.I. Pigment Blue 15: 6 dispersion was prepared as follows.

That is, C.I. Pigment Blue 15: 6 11.8 parts (average particle diameter 55 nm), a pigment dispersant BYK-161 (manufactured by BYK), and a mixed solution consisting of 82.3 parts of PGMEA are mixed and dispersed with a bead mill (zirconia beads 0.3 mm diameter) for 3 hours. A pigment dispersion liquid was prepared. Then, the dispersion | distribution process was performed as a flow volume of 500 g / min under the pressure of 2000 kg / cm <3> using the high pressure disperser NANO-3000-10 (made by Nippon Biei Co., Ltd.) with a pressure reduction mechanism. This dispersion treatment was repeated 10 times to obtain a pigment dispersion (C.I. Pigment Blue 15: 6 dispersion). It was 24 nm as a result of measuring the average primary particle diameter of the pigment about the obtained pigment dispersion liquid by the dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (made by Nikki Corporation)).

(3-2) Preparation of colored curable composition

Each following component was mixed and the colored curable composition was obtained.

Solvent: CyH… Part 1.133

Alkali-soluble resin: methacrylic acid benzyl / methacrylic acid copolymer (20% CyH solution)... 1.009 parts (molar ratio = 70: 30, weight average molecular weight 30000)

Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.). 0.225part

Surfactant: Solsperse 20000 (1% cyclohexane solution, Geneca) 0.125part

-Oxime photoinitiator (compound of the following structure) 0.087parts

Pigment multimer (example compound S-1)... 0.183parts

Pigment Blue 15: 6 dispersion… Part 2.418

(Solid content concentration 13.57%, pigment concentration 11.80%)

Surfactant: glycerol propoxylate (1% cyclohexane solution)... 0.048part

(4) Exposure, development (image formation) of colored curable composition

The colored curable composition obtained in the above (3) is applied onto the primer layer of the glass substrate on which the primer layer obtained in the above (2) is formed using a spin coater so that the film thickness after drying is 0.6 µm and prebaked at 100 ° C for 120 seconds. did.

Subsequently, exposure apparatus UX3100-SR (made by Ushio Denki Co., Ltd.) was used, and the coating film was irradiated with the exposure amount of 200 mJ / cm <2> through the mask of 2 micrometers of line widths at the wavelength of 365 nm. After exposure, it developed on 25 degreeC and 40 second conditions using the developing solution CD-2000 (made by Fujifilm Electronics Material Co., Ltd.). Then, after rinsing with running water for 30 seconds, it spray-dried. Then, post-baking was performed at 200 degreeC for 15 minutes.

(5) Evaluation

The heat resistance, solvent resistance, and light resistance of the coating film apply | coated on the glass substrate using the colored curable composition were evaluated as follows. The evaluation results are shown in Table 2 below.

[Heat resistance]

The glass substrate coated with the colored curable composition obtained in the above (3) was placed on a hot plate at 200 ° C so as to contact the substrate surface, and heated for 1 hour, followed by heating with a colorimeter MCPD-1000 (manufactured by Otsuka Denshi Co., Ltd.). Color difference ((DELTA) E ^* ab value) in back and front was measured, and it was set as the index which evaluates thermal fastness, and evaluated according to the following criteria. The smaller the value of ΔE ^* ab, the better the heat resistance. In addition, ΔE ^* ab value is a value obtained from the following color difference formula by CIE1976 (L ^* , a ^* , b ^* ) spatial colorimeter (Japanese Color Society: New Color Science Handbook (Showa 60) p.266) .

ΔE ^＊ ab = {(ΔL ^＊ ) ² + (Δa ^＊ ) ² + (Δb ^＊ ) ² } ^1/2

-Criteria-

◎: ΔE ^* ab value <3

0: 3 ≤ ΔE ^* ab value <5

Δ: 5≤ΔE ^* ab value≤15

×: ΔE ^* ab value> 15

[Solvent resistance]

Spectroscopy of various coating films after post-baking obtained in the above (4) was measured (spectral A). This coating film was prebaked by applying the resist solution A obtained in the above (1) so as to have a film thickness of 1 μm, and then using CD-2000 (manufactured by Fujifilm Electronics Materials) developer using a developer. The image development was carried out under the conditions of 占 폚 and 120 seconds, and the spectroscopy was measured again (spectral B). The pigment | dye persistence (%) was computed from the ratio of this spectral A, B, and this was made into the index which evaluates solvent resistance. The closer to 100%, the better the solvent resistance.

-Criteria-

○: Dye persistence> 90%

△: 70% ≤ dye remaining ratio ≤ 90%

X: Dye persistence <70%

[Light resistance]

Spectroscopy of various coating films after post-baking obtained in the above (4) was measured (spectral A). This coating film was irradiated with a xenon lamp at 100,000 lux for 20 hours (2 million lux. Equivalence). The color difference (ΔE ^* ab value) of the coating film before and after the xenon lamp irradiation was measured to be an index of light resistance. The smaller the ΔE ^* ab value is, the better the light resistance is, and the judgment criteria are as follows.

-Criteria-

◎: ΔE ^* ab value <3

○: 3≤ΔE ^* ab value <5

Δ: 5≤ΔE ^* ab value≤15

×: ΔE ^* ab value> 15

Examples 1-2-1 to 17 and Comparative Examples 1-1 to 1-2

In the preparation of the colored curable composition of Example 1-1, the pattern was changed in the same manner as in Example 1-1 except that Example Compound S-1 was changed (but equal mass) to the colorant described in Table 2 below. It formed and performed the same evaluation. The evaluation results are shown in Table 2. The structure of the comparative pigment | dye 1 of Table 2, and the comparative pigment | dye 2 (C.I. acid red 87) is shown below.

[Examples 2-1 to 2-17, Comparative Examples 2-1 to 2-2]

Using the colored curable compositions used in Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-2, respectively, a color filter was produced in the following order, and Examples 2-1 to 2-17 and Comparative Examples. Color conversion evaluation was performed as 2-1 to 2-2. The evaluation results are shown in Table 3 below.

-Production of monochromatic color filters

The colored curable composition used in Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-2 was dried on the glass substrate with the (2) primer layer produced in Example 1-1, respectively, and it dried It applied using the spin coater so that a film thickness might be set to 1 micrometer, and prebaked at 100 degreeC for 120 second, and the colored film was formed. An exposure amount and illuminance of 200 [mJ / cm 2] by an i-line stepper (Canon Co., Ltd. FPA-3000i5 +) through a mask pattern in which 7.0 µm square pixels are arranged in a 4 mm x 3 mm area on the substrate for this colored film. It exposed at 1200mW / cm <2> (integrated irradiation roughness). After exposure, paddle development was carried out at 23 ° C. for 60 seconds using a developing solution (CD-2000, manufactured by Fujifilm Electronics Materials Co., Ltd., 60%) to form a pattern. It was then rinsed with running water for 20 seconds and then spray dried. Then, the ultraviolet-ray of 10000 [mJ / cm <2>] was irradiated to the whole glass substrate with a pattern as a ultraviolet irradiation process after a developing process using the high pressure mercury lamp (Ushio Denki Co., Ltd. UMA-802-HC552FFAL). After irradiation, the post-baking process was performed on the hotplate for 300 second at 220 degreeC, and the coloring pattern was formed on the glass substrate. Moreover, the wavelength light of 275 nm or less contained in irradiation light from a high pressure mercury lamp is 10%.

Color conversion evaluation

CT-2000L solution (base transparent agent, Fujifilm Electronics Material Co., Ltd. product) was apply | coated to the colored pattern formation surface of the color filter produced as mentioned above so that a dry film thickness might be 1 micrometer, and it dried, After forming a transparent film, it heat-processed at 200 degreeC for 5 minutes. After the completion of heating, the absorbance of the transparent film adjacent to the colored pattern was measured by a brown rice spectrophotometer (LCF-1500M manufactured by Otsuka Denshi Co., Ltd.). The ratio [%] of the value of the absorbance of the obtained transparent film was computed about the absorbance of the coloring pattern measured before heating, and it was set as the index which evaluates color conversion.

-Criteria-

% Color conversion to adjacent pixels

◎: Color conversion <1% to neighboring pixels

○: 1% <color conversion to neighboring pixels≤10%

Δ: 10% ≤ color conversion to adjacent pixels ≤ 30%

X: Color conversion> 30% to neighboring pixels

As shown in Table 2 and Table 3, Examples 1-1 to 1-17 using the dye multimer of the present invention all exhibited excellent heat resistance, solvent resistance, and light resistance. Moreover, it turns out that the color conversion to the adjacent pattern was suppressed in all the Examples 2-1 to 2-17 using the dye multimer of this invention.

In addition, the colored curable composition which changed the photoinitiator in Example 1-1 to the compound OXE-01 and OXE-02 of the following structure, respectively, obtained the same result as Example 1-1, and obtained the oxime initiator The used colored curable composition showed that favorable heat resistance, solvent resistance, and light resistance were obtained.

In addition, both OXE-01 and OXE-02 are commercially available initiators of BASF Corporation.

Claims (11)

(a) a xanthene skeleton is included as a partial structure of a pigment | dye site | part, and also contains the dye multimer which has alkali-soluble group, (b) polymeric compound, (c) photoinitiator, and (d) organic solvent,
The said (a) dye multimer is a dye multimer represented by the following general formula (D), The colored curable composition for color filter manufacture characterized by the above-mentioned.

[N4 in general formula (D) represents the integer of 3-100,
L ⁴ is a substituted or unsubstituted arylene group, a substituted or unsubstituted heterocyclic linking group, or a substituted or unsubstituted alkylene linking group as a central mother nucleus, and a substituted or unsubstituted straight alkylene group having 1 to 30 carbon atoms , A substituted or unsubstituted branched or cyclic alkylene group having 3 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-,- S-, -NR- (R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), -C (= O)-, -SO-, -SO _2- , and are formed by connecting two or more thereof A divalent linking group selected from the group consisting of a linking group is substituted to represent a 3 to 100-valent linking group, and further includes -S-,
A plurality of Dye each independently represents a dye residue obtained by removing one hydrogen atom from the following general formula (M)]

[In General Formula (M), R <^1> , R <^2> , R <^3> , and R <^4> represent a hydrogen atom or a monovalent substituent each independently, R <^5> represents a monovalent substituent each independently, m is 0-5 Represents an integer] The method of claim 1,
n4 represents the integer of 3-40, The colored curable composition for color filter manufacture. The method of claim 1,
The weight average molecular weights of said (a) dye multimer are 5000-30000, The colored curable composition for color filter manufacture characterized by the above-mentioned. The method of claim 1,
The said alkali-soluble group is a carboxyl group or a sulfonic acid group, The colored curable composition for color filter manufacture characterized by the above-mentioned. The method of claim 1,
Said (c) photoinitiator is an oxime type compound, The colored curable composition for color filter manufacture characterized by the above-mentioned. The method of claim 1,
It is a colored curable composition for color filter manufacture for solid-state image sensors, The colored curable composition for color filter manufacture characterized by the above-mentioned. The method of claim 1,
n4 represents the integer of 3-10, The colored curable composition for color filter manufacture. It uses the colored curable composition for color filter manufacture in any one of Claims 1-7, The color filter characterized by the above-mentioned. The manufacturing method of the color filter characterized by apply | coating the coloring curable composition for color filter manufacture in any one of Claims 1-7 on a board | substrate, exposing through a mask, and developing to form a pattern shape. The color filter of Claim 8 is provided, The solid-state image sensor characterized by the above-mentioned. The color filter of Claim 8 is provided, The liquid crystal display device characterized by the above-mentioned.