KR102002323B1 - Colored curable composition, color filter, method of producing the same, solid state imaging device, liquid crystal display device, and pigment polymer - Google Patents

Abstract

Disclosed is a colored curable composition comprising a colorant multimer capable of forming a cured film having excellent color purity, light resistance, heat resistance, and solvent resistance, less color change, and good pattern formability.
(Solving Means) A colored curable composition comprising (a) a pigment multimer containing a xanthene skeleton as a partial structure of a pigment region, (b) a polymerizable compound, (c) a photopolymerization initiator, and (d) an organic solvent.

Description

COLORED CURABLE COMPOSITION, COLOR FILTER, SOLID STATE IMAGING DEVICE, LIQUID CRYSTAL DISPLAY DEVICE, AND PIGMENT POLYMER (COLORED CURABLE COMPOSITION, COLOR FILTER, METHOD OF PRODUCING THE SAME, SOLID STATE IMAGING DEVICE, LIQUID CRYSTAL DISPLAY DEVICE, AND PIGMENT POLYMER }

The present invention relates to a colored curable composition, a color filter, a production method thereof, a solid-state image pickup device, a liquid crystal display device, and a dye multimer suitable for the production of a color filter used for a liquid crystal display device or a solid-

As a method for producing a color filter for use in a liquid crystal display device or a solid-state image pickup device, there is a pigment dispersion method. As the pigment dispersion method, a pigmented curable composition in which pigments are dispersed in various photosensitive compositions is used, There is a method of manufacturing a filter. That is, the colored curable composition is coated on a substrate using a spin coater, a roll coater, or the like, and dried to form a coated film of the colored curable composition, and the colored film is obtained by pattern exposure and development of the coated film. The color filter is manufactured by repeating this operation for the desired color component.

Since the above method uses pigments, it is stable against light or heat, and patterning is performed by photolithography. Therefore, positional accuracy is sufficiently secured and it has been widely used as a preferable method for manufacturing color filters for liquid crystal displays.

On the other hand, in color filters for solid-state image pickup devices such as CCDs, higher definition has recently been desired. The pattern size tends to become finer with higher definition, but it has been considered that it is difficult to further improve the resolution by making the size of the pattern finer in the conventionally widely used pigment dispersion method. One of the reasons is that, in the case of a fine pattern, coarse particles produced by agglomeration of pigment particles cause color unevenness. Therefore, recently, the pigment dispersion method, which has been generally used so far, has become unsuitable for applications requiring fine patterns such as solid-state image pickup devices.

In order to achieve high definition and high resolution under the background described above, it has been studied to use dyes as colorants (for example, see Patent Document 1). However, the dye-containing colored curable composition has the following new problems. In other words,

(1) Dyes in a molecular dispersed state generally have lower light resistance and heat resistance than pigments that are a molecular aggregate.

(2) Dyes in a molecular dispersion state generally have poor solvent resistance as compared with a pigment as a molecular aggregate.

(3) The dye often exhibits an interaction with other components in the colored curable composition, and it is difficult to control the solubility (developability) of the cured portion and the non-cured portion,

(4) When the molar extinction coefficient (?) Of the dye is low, it is necessary to add a large amount of dye, so that other components such as a polymerizable compound (monomer), a binder and a photopolymerization initiator in the colored curable composition can not be reduced The curability of the colored curable composition, the heat resistance after curing, the developability after exposure, and the like are deteriorated.

Among the problems of dyes, there are (4) xanthenes (see, for example, Patent Document 2) as a dye for solving the molar extinction coefficient (?) Of a dye, but a compound whose light resistance and heat resistance are lower than other dyes The improvement is strongly demanded.

Further, the colored curable composition containing a dye has a problem of color conversion other than the above-mentioned problems. For example, in order to form a red pixel on the formed green pixel, a colored curable composition containing a red dye is applied on the green pixel and the red curable composition layer of the unexposed red light on the green pixel is developed and removed, Or a phenomenon in which a dye in a red colored curable composition shifts to a green pixel and a green pixel is discolored or discolored or a green pixel is reddish, a so-called " color conversion " Is strongly desired.

Further, in the colored curable composition containing the dye, when the colored pixel is heated in the process of manufacturing the color filter forming the colored pixel, the process of installing the color filter in the solid-state image pickup device, etc., the dye tends to sublimate in addition to the problem of the heat resistance of the dye , There is a problem that the colored pixels are discolored or discolored by the sublimation of the dyes, and a desired hue can not be obtained. In addition, there is also a problem that the sublimation dye contaminates the manufacturing process. As a technique for preventing this, there has been proposed to use a dye imparted with a polymerizable group in a colored curable composition (see, for example, Patent Document 3), but the above-mentioned color conversion and the like are not sufficiently effective, Improvement was desired.

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

A colored curable composition containing a xanthene as a dye has been required to have superior light resistance and heat resistance. Further, as described in Problem (2) above, it has been required to improve the solvent resistance in order to use a dye as a coloring component.

The solvent resistance is a property in which the colored component in the hardened portion is retained in the colored pixel without being eluted into the solvent. When an RGB color filter is manufactured by a photolithography method, a colored pattern is covered with a colored curable composition having a different color in order to sequentially form respective color patterns. At this time, when the coloring component in the cured portion is eluted into the colored curable composition of the next color, or when the dye contained in the colored curable composition of the next color shifts to the colored pixel, High solvent resistance is required for parts. In this respect, the dye is in a molecular dispersion state, and the solvent resistance is lower than that of the pigment forming the aggregate with strong intermolecular force.

Further, in the production of the color filter, since the heat treatment is performed to increase the degree of curing of the colored pattern after the application, the exposure and the development, the fixability of the dye in the cured part also becomes a problem. Dyestuffs that are in the molecular dispersion state can move with a smaller thermal energy than the pigment aggregates of the molecular aggregate, so that it is easy to perform color conversion into adjacent patterns having different colors.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to achieve the following objects.

That is, a first object of the present invention is to provide a colored curable composition comprising a colorant multimer capable of forming a cured film having excellent color purity, light resistance, heat resistance, and solvent resistance, have.

A second object of the present invention is to provide a color filter having a coloring pattern excellent in color purity, heat resistance and light fastness even in the case of a thin layer, a method of manufacturing the color filter, a solid- .

A third object of the present invention is to provide a colorant-polymerizable composition which is excellent in color purity, light resistance, heat resistance, and solvent resistance, has little color change, and is capable of forming a colored curable composition having good pattern formability.

The inventors of the present invention have studied various pigments in detail and found that a xanthene compound having a specific structure has a good color and a high extinction coefficient and that the xanthene skeleton is introduced into a pigment multimer, Can provide a colored curable composition having a high solvent resistance and a reduced color conversion by introducing a polymerizable monomer as a polymerization component and introducing an alkali-soluble group into the dye multimer as required, It is possible to provide a colored curable composition having excellent (low concentration dependence of alkali developing solution), and the present invention has been achieved on the basis of this finding.

Specific means for solving the above problems are as follows.

(1) A colored curable composition comprising a pigment multimer containing (a) a xanthene skeleton as a partial structure of a pigment region, (b) a polymerizable compound, (c) a photopolymerization initiator, and (d) an organic solvent.

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

Wherein R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a monovalent substituent, each R ⁵ independently represents a monovalent substituent, m is an integer from 0 to 5, Quot;

(3) The colorant multimer of (1) or (2), which contains at least one of the structural units represented by the following general formula (A), general formula (B) , Or a colorant-curable composition represented by the general formula (D).

[Formula (A) of the X ¹ represents a linking group formed by polymerization, L ¹ represents a single bond or a divalent connecting group, Dye has the general formula 1, remove the dye moiety to any of a hydrogen atom from the (M) Gt;

[Formula (B) of X ² represents a connecting group formed by a polymerization, L ² represents a single bond or a divalent linking group, A represents a group capable Dye and ionic bond, or coordinate bond, Dye has the formula ( M) by removing one hydrogen atom to form a dye residue capable of ionic bonding or coordination bonding with A]

[In the general formula (C), L ³ represents a single bond or a divalent linking group, and when plural L ³ exist, the structure of L ³ may be the same or different. Dye represents a pigment residue in which two arbitrary hydrogen atoms have been removed from the above general formula (M). n3 represents an integer of 1 to 4]

[In the general formula (D), L ⁴ represents a linking group of an n4 valent, n4 represents an integer of 2 to 100, and a plurality of Dye each independently represents a dye residue obtained by removing one arbitrary hydrogen atom from the general formula (M) Gt;

&Lt; 4 > The colored curable composition according to any one of < 1 > to < 3 >, wherein the pigment (a) further comprises an alkali-soluble group.

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

<6> A color filter comprising the colored curable composition according to any one of <1> to <5>.

&Lt; 7 > A process for producing a color filter, comprising applying a colored curable composition according to any one of < 1 > to < 5 > onto a substrate, exposing through a mask, and developing the pattern to form a patterned image.

&Lt; 8 > A solid-state imaging device comprising the color filter according to < 6 >.

&Lt; 9 > A liquid crystal display device comprising the color filter according to < 6 >.

&Lt; 10 > A dye multimer containing a dye skeleton derived from a xanthene compound represented by the following general formula (M) as a partial structure of a dye part.

Wherein R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a monovalent substituent, each R ⁵ independently represents a monovalent substituent, m is an integer from 0 to 5, Quot;

The present invention is characterized in that a pixel pattern is formed in a thin film (for example, a thickness of 1 mu m or less), and a high definition (for example, 0.5 to 2.0 mu m in side length of a pixel pattern viewed from the substrate normal direction) And is particularly effective for forming a color filter for a solid-state image pickup device in which a desired rectangular cross-sectional profile is required.

According to the present invention, it is possible to provide a colored curable composition comprising a colorant multimer capable of forming a cured film having excellent color purity, light resistance, heat resistance, and solvent resistance, less color change, and good pattern formability.

Further, it is possible to provide a color filter having a coloring pattern excellent in color purity, heat resistance, and light fastness, a method of manufacturing the color filter, a solid-state image pickup device having the color filter, and a liquid crystal display device, even when being thin.

Further, it is possible to provide a colorant multimer capable of forming a colored curable composition having excellent color purity, light resistance, heat resistance, and solvent resistance, less color change, and good pattern formability.

Hereinafter, the colored curable composition, the color filter, the method for producing a color filter, the solid-state image pickup device, the liquid crystal display, and the dye multimer are described in detail. The following description of the constituent elements described below may be made on the basis of exemplary embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, the numerical range indicated by using &quot; ~ &quot; means a range including numerical values before and after &quot; ~ &quot; as a lower limit value and an upper limit value.

The colored curable composition of the present invention is characterized by containing a pigment multimer containing (a) a xanthene skeleton as a partial structure of a dye region, (b) a polymerizable compound, (c) a photopolymerization initiator, and (d) an organic solvent .

A pigment multimer containing (a) a xanthene skeleton used as a partial structure of a pigment part in the colored curable composition of the present invention will be described.

&Quot; (a) a dye multimer containing a xanthene skeleton as a partial structure of a dye site &quot;

The dye multimer in the present invention is a dye multimer containing a xanthene skeleton, which will be described in detail below, as a partial structure of a dye portion. The method of introducing the xanthene skeleton into the pigment multimer of the present invention may be any method. Polymerization may be carried out by polymerizing or copolymerizing a polymerizable monomer introduced with a xanthene skeleton to form a multimer, A xanthene skeleton may be introduced.

As a preferable embodiment, a multimer comprising at least one structural unit represented by the above-mentioned general formula (A), the general formula (B) or the general formula (C), or a multimer composed of a pigment multimer represented by the general formula (D) .

&Lt; Preferred physical properties of dye multimer in the present invention >

The dye multimer of the present invention can form a cured film having excellent color purity, light resistance, heat resistance, and solvent resistance, less color change, and good pattern formability, and therefore can be used for a colored curable composition . From such a point of view, in view of the desirable physical properties of the dye multimer in the present invention, when the dye multimer of the present invention is applied to the colored curable composition, the colorant multimer Is preferably an alkali-soluble group.

The method for introducing an alkali-soluble group into the polymeric multimer of the present invention is not particularly limited, but it can be introduced by synthesizing a pigment oligomer using a monomer having an alkali-soluble group, or after synthesizing a colorant oligomer, Group can be introduced.

When a dye multimer is synthesized using a monomer having an alkali-soluble group, a dye multimer comprising at least one of the structural units represented by the general formula (A), the general formula (B) or the general formula (C) Or at least one of the dye oligomers represented by the general formula (D) may have an alkali-soluble group. When the constituent unit represented by the general formula (A), the general formula (B) or the general formula (C) is a monomer having an alkali-soluble group, the Dye moiety (dye residue) may have an alkali-soluble group. From the viewpoint of compatibility, it is preferable that at least one of the other ethylenically unsaturated bond-containing monomers contained as a copolymerization component is a monomer having an alkali-soluble group, as compared with the monomer forming the constituent unit having the Dye moiety (dye residue).

The preferred alkali-soluble group of the dye multimer in the present invention is a carboxyl group, a sulfonic acid group, a phosphonic acid group, a hydroxyl group or a sulfonimide group, and preferably a carboxyl group or a sulfonic acid group.

Preferable examples of other ethylenic unsaturated bond-containing monomers which are included as the copolymerization component of the dye multimer include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and? -Methyl-p-carboxystyrene; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid, methacryloxyethylphosphonic acid, styrenesulfonic acid and p-hydroxystyrene, and acrylic acid and methacrylic acid are preferable.

The dye multimer of the present invention preferably contains an acid value of 10 to 400 mgKOH / g, more preferably an acid value of 30 to 300 mgKOH / g, from the viewpoint of coloring pattern forming property when applied to a colored curable composition, It is more preferable that the acid value is 50 to 200 mg KOH / g.

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

The dye multimer of the present invention preferably has a solubility in an alkali solution (pH 9 to 15) of 0.1 mass% or more and 80 mass% or less, more preferably 0.5 mass% or more and 50 mass% or less, or more preferably 1 mass% or more And more preferably 30 mass% or less. By being in this region, it is possible to form a desirable shape when the dye multimer of the present invention is used for an application requiring alkali development such as a colored curable composition, or to reduce residues on the substrate.

The dye multimer in the present invention is preferably dissolved in the following organic solvent. Examples of the organic solvent include esters (e.g., methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate and the like), ethers (such as methylcellosolve acetate (Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), aromatic hydrocarbons (for example, methyl ethyl ketone, And more preferably 5% by mass or more and 40% by mass or less, more preferably 10% by mass or less, and most preferably 10% by mass or less, Or more and 30 mass% or less. By being in this region, it is possible to obtain a desired application surface shape when the dye multimer of the present invention is applied to a colored curable composition or the like, and to reduce the concentration decrease due to elution after application of the colored curable composition of a colored color.

The Tg of the dye multimer in the present invention is preferably 50 DEG C or higher, more preferably 100 DEG C or higher. Further, the 5% mass reduction temperature by the thermal mass analysis (TGA measurement) is preferably 120 ° C or higher, more preferably 150 ° C or higher, and even more preferably 200 ° C or higher. By being in this region, it is possible to reduce the concentration change due to the heating process when the dye multimer of the present invention is applied to the colored curable composition or the like.

The maximum absorption wavelength (? Max) of the dye multimer in the present invention is preferably 510 nm or more and 590 nm or less, more preferably 530 nm or more and 570 nm or less, and more preferably 540 nm or more and 555 nm or less. By being in this region, a color filter having good color reproducibility can be produced when it is applied to a colored curable composition or the like. The absorbance of the dye multimer of the present invention at 450 nm is preferably 1,000 times or more, more preferably 10,000 times or more, and further preferably 100,000 times or more the absorbance at the maximum absorption wavelength (? Max). With this ratio in this range, it is possible to form a color filter having a higher transmittance, especially when a blue color filter is produced, when the dye multimer of the present invention is applied to a colored curable composition or the like.

The absorption coefficient per unit mass of the dye multimer in the present invention (hereinafter, referred to as ε '= ε / average molecular weight, unit: L / g · cm) is preferably 30 or more, And more preferably 100 or more. Within this range, a color filter having excellent color reproducibility can be produced when a color filter is produced by applying a dye multimer in the present invention to a colored curable composition.

Further, it is more preferable that the dye multimer of the present invention simultaneously satisfies the maximum absorption wavelength (? Max) of the dye multimer and the preferable range of the extinction coefficient per unit weight.

The molecular weight of the dye multimer in the present invention is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and still more preferably 5,000 to 20,000. Within this range, the effect of the present invention can be exhibited without fail, the solubility in a solvent is good, and the film (coloring pixel) of the obtained colored curable composition obtained by curing has good light resistance, heat resistance, and solvent resistance.

&Lt; Structure of the dye multimer in the present invention >

Hereinafter, the structure of the dye multimer in the present invention will be described in detail.

The dye multimer of the present invention includes a xanthene skeleton as a partial structure of a dye portion.

The dye multimer of the present invention is preferably a chroman skeleton derived from a xanthene compound wherein the xanthene skeleton is represented by the following formula (M).

&Lt; The xanthene compound represented by the general formula (M) >

A preferred form of the dye multimer in the present invention is a dye multimer containing a dye chain skeleton derived from a xanthene compound represented by the following formula (M) as a partial structure of a dye site.

In formula (M), R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a monovalent substituent, R ⁵ independently represents a monovalent substituent, and m represents an integer of 0 to 5 .

Examples of the monovalent substituent when R ¹ to R ⁴ and R ⁵ in the general formula (M) represent a monovalent substituent include a halogen atom (e.g., a fluorine atom, a chlorine atom and a bromine atom) , An alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms, more preferably a 1 to 24 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, A cyclohexyl group, a 1-norbornyl group, a 1-adamantyl group, a 1-adamantyl group, a 1-adamantyl group, a 1-adamantyl group, a 1-adamantyl group, An allyl group, a 3-butene-1-yl group), an aryl group (preferably an alkenyl group having a carbon number of 2 to 48, more preferably an alkenyl group having a carbon number of 2 to 18, Is an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group Preferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, and examples thereof include a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, , A 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group and a benzotriazol-1-yl group), a silyl group (preferably having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms Silyl group such as a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, a t-hexyldimethylsilyl group), a hydroxyl group, a cyano group, a nitro group, an alkoxy group Preferably 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, , A dodecyloxy group, and a cycloalkyloxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group), an aryloxy group (preferably having 6 to 48 carbon atoms, More preferably an aryloxy group having 6 to 24 carbon atoms such as a phenoxy group and a 1-naphthoxy group), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 18 carbon atoms A heterocyclic oxy group, for example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group)

A silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, a diphenylmethylsilyloxy group) , An acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, and more preferably a 2 to 24 carbon atoms, such as an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group) An alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, Cycloalkyloxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, Lt; / RTI &gt; is, for example, phenoxycarbonyloxy), Carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group), a sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably a sulfamoyloxy group having 1 to 24 carbon atoms, , N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, , Methylsulfonyloxy group, hexadecylsulfonyloxy group, cyclohexylsulfonyloxy group),

An arylsulfonyloxy group (preferably having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, Preferably an acyl group having 1 to 24 carbon atoms, such as a formyl group, an acetyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group and a cyclohexanoyl group), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, More preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyl Oxycarbonyl group), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably a carbon number 7 to 24, such as phenoxycarbonyl group), a carbamoyl group (preferably carbon An N, N-diethylcarbamoyl group, an N-ethyl-N-octylcarbamoyl group, a N, N, N-dimethylcarbamoyl group, a carbamoyl group having 1 to 24 carbon atoms, N-methylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), an amino group (preferably a carbon number More preferably an amino group having a carbon number of 24 or less, such as an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, a 2-ethylhexylamino group or a cyclohexylamino group)

An anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as an anilino group and an N-methylanilino group), a heterocyclic amino group And more preferably 1 to 18 carbon atoms, for example, a 4-pyridylamino group), a carbanamide group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms An amide group, for example, an acetamide group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexanamide group), an ureido group (preferably having 1 to 32 carbon atoms, more preferably 1 to 32 carbon atoms, (For example, ureido, N, N-dimethylureido, N-phenylureido), an imide group (preferably an imido group having not more than 36 carbon atoms, more preferably not more than 24 carbon atoms , For example, an N-succinimide group, an N-phthalimide group) , An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably a carbon number 2 to 24, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycar A cyclohexyloxycarbonylamino group), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably a carbon number 7 to 24, and an aryloxycarbonylamino group, For example, a phenoxycarbonylamino group), a sulfonamide group (preferably a sulfonamido group having 1 to 48 carbon atoms, more preferably a 1 to 24 carbon atoms, such as a methanesulfonamide group, a butanesulfonamide group , A benzenesulfonamide group, a hexadecanesulfonamide group, a cyclohexanesulfonamide group), a sulfamoylamino group (preferably having 1 to 48 carbon atoms, more preferably a sulfamoyl group having 1 to 24 carbon atoms (Preferably N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms An azo group, for example, phenyl azo group, 3-pyrazolyl azo group),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably a carbon number 1 to 24, such as methylthio group, ethylthio group, octylthio group, cyclohexylthio group) (Preferably an arylthio group having from 6 to 48 carbon atoms, and more preferably from 6 to 24 carbon atoms, such as a phenylthio group), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, Benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), an alkylsulfinyl group (preferably having 1 to 32 carbon atoms, preferably 1 to 30 carbon atoms, More preferably an alkylsulfinyl group having 1 to 24 carbon atoms, such as a dodecansulfinyl group), an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably a carbon number 6 to 24, For example, a phenylsulfinyl group), an alkylsulfonyl group (preferably having 1 to 48 carbon atoms, Preferably an alkylsulfonyl group having 1 to 24 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonyl group, a hexadecylsulfonyl group, An arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, and more preferably a carbon number of 6 to 24, such as phenylsulfonyl group, 1-naphthylsulfonyl group, ), A sulfamoyl group (preferably a sulfamoyl group having not more than 32 carbon atoms, more preferably not more than 24 carbon atoms, such as sulfamoyl group, N, N-dipropylsulfamoyl group, Ethylhexyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms And includes, for example, a phenoxyphosphonyl group, an octyloxyphosphonyl group, (Preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a diethoxyphosphinoylamino group, a dioctyloxyphosphinoylamino group), a phosphinoylamino group .

When the monovalent substituent represented by R ¹ to R ⁵ in the general formula (M) is a substitutable group, it may further have a substituent described in R ¹ to R ^{5. When} two or more substituents are present, The same or different.

R ¹ and R ² in the general formula (M), R ³ and R ⁴ , and R ^{5 in the} case where m is 2 or more are bonded to each other independently to form a 5-membered, 6-membered or 7-membered ring or an unsaturated ring May be formed. When the 5-membered, 6-membered, and 7-membered rings formed are also substitutable groups, they may be substituted with the substituents described in R ¹ to R ⁵ , and when they are substituted with two or more substituents, these substituents may be the same or different good.

In the formula (M), R ¹ and R ² , R ³ and R ⁴ , and R ⁵ when m is 2 or more are bonded to each other independently to form a 5-membered, 6-membered or 7-membered ring having no substituent , Or a 5-membered, 6-membered or 7-membered ring or unsaturated ring having no substituent when forming an unsaturated ring includes, for example, a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, A thiazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, a cyclohexane ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring. .

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. Further, the maximum absorption wavelength? Max is preferably from 520 nm to 580 nm, and more preferably from 530 nm to 570 nm from the viewpoint of improving the color purity. Further, the maximum absorption wavelength and the molar extinction coefficient are those measured by a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).

The melting point of the compound having a xanthene skeleton represented by the general formula (M) is preferably not excessively high in view of solubility.

The compound having a xanthene skeleton represented by the above general formula (M) can be synthesized by a method described in the literature. Specifically, the method described in Tetra Head Letter, 2003, vol.44, No. 23, pages 4355 to 4360, Tetrahedron, 2005, vol.61, No. 12, pages 3097 to 3106 .

A more preferable dye multimer in the present invention will be described.

As the dye multimer containing the xanthene skeleton as a partial structure of the dye region, a dye multimer containing at least one of the constitutional units represented by the following general formulas (A), (B) and (C) , Or a dye multimer represented by the general formula (D). These will be explained sequentially.

&Lt; Structural unit represented by general formula (A)

In the 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 formula (M) .

In the general formula (A), X ¹ represents a linking group formed by polymerization. That is, a part forming a repeating unit corresponding to a main chain formed by a polymerization reaction. In addition, a portion sandwiched by two * is a repetitive unit. X ¹ is 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 the like, and is preferably a linking group formed by polymerizing an unsaturated ethylene group. Specifically, the following linking groups and the like can be mentioned, but the linking groups formed by polymerization in the present invention are not limited to these.

Further, in the following (X-1) to (X-15), L ¹ is connected at a site indicated by *.

In the general formula (A), L ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group when L ¹ represents a divalent linking group include a substituted or unsubstituted linear or branched alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a butyl A substituted or unsubstituted arylene group having 6 to 30 carbon atoms (e.g., a phenylene group or a naphthalene group), a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S -, -NR-, -C (= O) -, -SO-, -SO ₂ -, a linking group represented by the following formula (2), a linking group represented by the following formula (= O) -, -OC (= O) -, -C (= O) - or a linking group formed by connecting two or more of these groups (for example, N (R) -, -C (= O) O-, wherein R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. The bivalent linking group in the general formula (A) is not limited in any way as long as it can exhibit the effect 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 an integer of 0 to 4; When k is 2 or more, R ³ may be the same or different. * In the formulas (2) to (4) represents a position at which the compound bonds with the X ¹ group in the formula (A), and ** represents a position at which the compound bonds with Dye in the formula (A)

In the general formula (A), Dye represents a pigment residue in which one hydrogen atom has been removed from the general formula (M).

Specific examples of the structural unit represented by the general formula (A) are shown below, but the present invention is not limited thereto.

&Lt; Structural unit represented by general formula (B) >

Next, the structural units represented by the general formula (B) will be described in detail.

In the general formula (B), X ² represents a linking group formed by polymerization, L ² represents a single bond or a divalent linking group, A represents a group capable of ionic or coordination bonding with Dye, ) By removing one hydrogen atom to form a dye residue capable of ionic bonding or coordination bonding with A.

The group represented by X ² in the general formula (B), and L ² each represent the same group as X ¹ and L ^{1 in} the general formula (A), and the preferable range is also the same.

The group represented by A in the general formula (B) may be a group capable of ionic or coordinate bonding with Dye, and the group capable of ionic bonding may be either an anionic group or a cationic group. 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 acyl sulfonamide group or a sulfonimide group, more preferably a pKa of 7 or less, and further preferably 5 or less.

Specific preferred examples of the anionic group are shown below, but the present invention is not limited thereto. In the anionic groups shown below, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

As the cationic group represented by A in the 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 or a phosphonium group) And a substituted ammonium group is particularly preferable.

Specific preferred examples of the cationic group are shown below, but the present invention is not limited thereto. In the following cationic groups, R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Specific examples of the structural unit represented by the formula (B) are shown below, but the present invention is not limited thereto.

&Lt; Structural unit represented by general formula (C)

Next, the structural units represented by the general formula (C) will be described in detail.

In the general formula (C) L ³ represents a single bond or a divalent linking group, if present, the plural L ³ is the structure of the L ³ is gatahdo or different. Dye represents a pigment residue in which two arbitrary hydrogen atoms have been removed from the above general formula (M). n3 represents an integer of 1 to 4;

Examples of the divalent linking group represented by L ³ in the general formula (C) include a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (e.g., a methylene group, an ethylene group, a trimethylene group, a propylene group , A substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (e.g., a phenylene group or a naphthalene group) -S-, -NR-, -C (= O ) -, -SO-, -SO 2 -, and, for these linking group formed by linking two or more (for example, -N (R) C (= O) (= O) -, -C (= O) N (R) -, -C (= O) O-, -N (R) C . In the above formulas, R in each formula independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Specific examples which are preferably used as the divalent linking group represented by L ³ in the general formula (C) are described below, but L ³ of the present invention is not limited to these.

Specific examples of the structural unit represented by the formula (C) are shown below, but the present invention is not limited thereto.

&Lt; Copolymerization component &

The dye multimer in the present invention may be formed of only the constituent unit represented by the above-mentioned formula (A), the formula (B) or the formula (C), but may be made larger in amount together with other constituent units. As the other structural units, preferred are the structural units shown below, and specific examples thereof are shown, but the present invention is not limited thereto.

&Lt; Colorant mass represented by general formula (D) >

Next, the dye multimer represented by the formula (D) will be described in detail.

In the general formula (D), L ⁴ represents a linking group of n4, n4 represents an integer of 2 to 100, and a plurality of Dye each independently represents a dye residue obtained by removing one arbitrary hydrogen atom from the general formula (M) .

In the general formula (D), n4 is preferably 2 to 80, more preferably 2 to 40, and particularly preferably 2 to 10.

Examples of the divalent linking group represented by L ⁴ in the general formula (D) when n ⁴ is 2 include a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (for example, a methylene group, (E.g., a phenylene group, a naphthalene group, etc.), a substituted or unsubstituted heterocyclic linking group, a -CH = CH -, -O-, -S-, -NR-, -C (= O) -, -SO-, -SO ₂ -, and a linking group formed by connecting two or more thereof, ), -C (= O) -, -OC (= O) -, -C (= O) N (R) ) - etc.] can be preferably used. In the above formulas, R in each formula independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Examples of the connecting group of n4 having n4 of 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 and the like) (For example, a 1,3,5-triazine group, etc.), an alkylene linking group or the like as a central nucleus and substituting the bivalent linking group.

Specific examples of the dye multimer represented by the general formula (D) are shown below, but the present invention is not limited thereto.

Hereinafter, preferred examples of the pigment multimer in the present invention are shown in Table 1 below, including the constituent unit (the above constituent unit), the copolymer mass ratio, the weight average molecular weight and the degree of dispersion.

The dye multimer in the present invention preferably contains a structural unit represented by the general formula (A), the general formula (B) or the general formula (C) as a part thereof, Is preferably contained.

The dye multimer of the present invention is a dye multimer containing 100 mass% (mass%) of the constituent unit represented by the formula (A), the formula (B) or the formula (C) May be a polymerized product obtained by polymerizing only the constituent unit represented by the general formula (A), the general formula (B) or the general formula (C).

From the viewpoint of coloring power, it is preferable that the constituent unit represented by the general formula (A), the general formula (B) or the general formula (C) is contained in a mass ratio (mass%) in the pigment mass of 10 mass% to 100 mass% , More preferably 20 mass% to 100 mass%, and still more preferably 30 mass% to 100 mass%.

The method for synthesizing a dye multimer in the present invention will be described taking S-4 as an example as described above.

<Synthesis of Exemplified Compound S-4>

23 g (0.034 mol) of commercially available xanthene dye (Acid Red 289; Tokyo Kasei Hing) was added to sulfolane (150 ml), and 40 g (0.34 mol) of chlorosulfonic acid was added dropwise while stirring at 5 캜. This solution was heated to an internal temperature of 80 占 폚, and stirred at that temperature for 4 hours. After the temperature of the reaction solution was lowered to about 30 캜, 40 g (0.34 mol) of thionyl chloride was slowly added dropwise, and the mixture was heated to 80 캜 and stirred for 4 hours. The reaction solution was poured into ice water, and the precipitated acid chloride solids were separated by filtration and dried.

Separately, 2-aminoethanol (1.2 g, 0.02 mol) dissolved in acetonitrile was cooled to an internal temperature of 5 캜, and the obtained acid chloride derivative was gradually added. The temperature of the reaction solution was raised to 40 캜, 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).

The alcohol was dissolved in N, N-dimethylacetamide (50 ml), methacrylic chloride was added thereto at 5 占 폚, and the mixture was stirred for 3 hours. The reaction solution was poured into water, and the precipitated crystals were separated by filtration and dried to obtain Q-1 form (4.7 g, 0.0072 mol).

The resulting 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) , 2'-azobis (2-methylpropionate) (0.2 g) in 1 g of PGMEA was added dropwise over 3 hours. After 4 hours from the start of the dropwise addition, dimethyl 2,2'-azobis (2-methylpropionate) (0.2 g) was added and stirring was continued at 85 ° C for additional 2 hours. To the reaction solution, 200 ml of PGMEA and 200 ml of methanol were added, and this was added dropwise to ice water with stirring. The precipitated crystals were filtered, and the obtained crystals were dried under reduced pressure to obtain 3.9 g of Exemplified Compound S-4.

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

The molecular weight of the dye multimer in the present invention is preferably in the range of 5000 to 30,000 and the number average molecular weight (Mn) in the range of 3,000 to 20,000 in weight average molecular weight (Mw). More preferably, the weight average molecular weight (Mw) is in the range of 5000 to 25000 and the number average molecular weight (Mn) is in the range of 3000 to 17000. Particularly preferably, the weight average molecular weight (Mw) is in the range of 5,000 to 20,000, and the number average molecular weight (Mn) is in the range of 3,000 to 15,000.

From the viewpoint of developability when the colorant multimer of the present invention is applied to the colored curable composition and a color filter is produced, the weight average molecular weight (Mw) of the specific polymer is preferably 20,000 or less.

&Quot; Coloring curable composition &

The colored curable composition of the present invention contains at least one kind of the above-mentioned pigment multimer in the present invention as a colorant, and further contains (b) a polymerizable compound, (c) a photopolymerization initiator, and (d) an organic solvent. The colored curable composition of the present invention is characterized in that it is cured by heat, light or both, and may be constituted by using other components such as a binder and a crosslinking agent, if necessary.

Depending on the characteristics of the compound having a xanthene skeleton as a partial structure of the pigment region, the coloring and curing composition of the present invention can be formed into a thin film (for example, a thickness of 1 mu m or less) as a pixel pattern. Therefore, the colored curable composition of the present invention is required to have high clarity of a minute size of 2 占 퐉 or less (the side length of the pixel pattern viewed from the normal direction of the substrate is, for example, 0.5 to 2.0 占 퐉), and a satisfactory rectangular cross- Is particularly preferable for manufacturing a color filter for a solid-state image sensor.

In the tinting curable composition of the present invention, the above-mentioned colorant multimer may be used singly or in combination of two or more kinds.

The content of the dye multimer in the color-curable composition of the present invention varies depending on the molecular weight and the molar extinction coefficient of the dye multimer, but is preferably from 10% by mass to 70% by mass with respect to the total solid component of the colored curable composition, , More preferably from 10% by mass to 50% by mass, and most preferably from 15% by mass to 30% by mass.

The coloring curable composition of the present invention and the color filter using the coloring curable composition may also use colorants other than the dye multimer as long as the effect of the present invention is not impaired. (For example, CI Acid Blue 7, CI Acid Blue 83, CI Acid Blue 90, CI Solvent Blue 38, CI Acid Violet 17, CI Acid Blue), which has an absorption maximum at 550 nm to 650 nm Violet 49, CI Acid Green 3 and the like), xanthene-based pigments having an absorption maximum in the range of 500 nm to 600 nm, for example, CI Acid Red 289 and the like can be used.

The content of the triarylmethane-based coloring agent is not particularly limited so long as the effect of the present invention is not impaired. The content of the triarylmethane-based coloring agent is preferably 0.5% by mass to 50% by mass relative to the total solid content of the color-curable composition of the present invention.

Further, in order to produce a blue filter array, it is preferable to use at least one pigment and a phthalocyanine pigment in combination.

(Phthalocyanine-based pigment)

The phthalocyanine-based pigment usable in the present invention is not particularly limited as long as it is a pigment having a phthalocyanine skeleton. The central metal contained in the phthalocyanine-based pigment is not particularly limited as long as it is a metal capable of forming a phthalocyanine skeleton. Among them, magnesium, titanium, iron, cobalt, nickel, copper, zinc and aluminum are preferably used as the central 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, chloroaluminum 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 preferable, and C.I. Pigment Blue 15: 6 is preferred.

The content of the phthalocyanine pigment in the coloring and curing composition of the present invention is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and still more preferably 35% by mass, based on the total solid content of the colored curable composition. And most preferably from about 50% by mass to about 50% by mass.

The content ratio of the pigment multimer having the xanthene skeleton as a partial structure of the pigment part and the phthalocyanine pigment is represented by the ratio of the pigment multimer having the xanthene skeleton as a partial structure of the pigment part, the phthalocyanine pigment: 100: 5 to 100: 100, more preferably 100: 15 to 100: 75, and further preferably 100: 25 to 100: 50.

(Dispersant)

The tinting curable composition of the present invention may contain a dispersing agent when it contains a pigment.

Examples of the pigment dispersant usable in the present invention include polymer dispersants such as polyamide amines and salts thereof, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates (Meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkylphosphoric acid ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like.

Polymeric dispersants can be further divided into linear polymers, end-modified polymers, graft-type polymers, and block-type polymers from the structure.

The polymer dispersant is adsorbed on the surface of the pigment to prevent re-aggregation. Therefore, an end-modified polymer having an anchor portion on the surface of the pigment, a graft-type polymer, and a block-type polymer can be mentioned as preferable structures.

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

Examples of the terminal modified polymer having an anchor site on the surface of the pigment include polymers having a phosphate group at the terminals described in JP-A-3-112992 and JP-A-2003-533455, JP-A-2002-273191 Polymers having a sulfonic acid group at the terminals described in JP-A No. 9-77994, etc., and polymers having a partial skeleton of an organic dye or a heterocyclic ring. Further, a polymer having an anchor moiety (an acid group, a basic group, a partial skeleton of an organic dye, a heterocycle, etc.) on the surface of two or more pigments at the polymer terminal described in Japanese Patent Application Laid-Open No. 2007-277514 is also excellent in dispersion stability desirable.

Examples of the graft polymer having an anchor portion on the surface of the pigment include poly (lower alkylene) polymers described in Japanese Patent Application Laid-open No. 54-37082, Japanese Patent Application Laid-Open Nos. 8-507960 and 2009-258668, Imine) and polyester, reaction products of polyallylamine and polyester described in Japanese Patent Application Laid-Open No. 9-169821, etc., and macroscopies disclosed in Japanese Patent Application Laid-Open Nos. 10-339949 and 2004-37986 A graft polymer having a partial skeleton of an organic dye or a heterocyclic ring described in JP-A-2003-238837, JP-A-2008-9426, and JP-A-2008-81732, etc., copolymer of a monomer and a nitrogen atom monomer , A copolymer of a macromonomer and an acid group-containing monomer described in JP-A-2010-106268, and the like. Particularly, the positive dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 is particularly preferable from the viewpoints of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored curable composition using the pigment dispersion.

Known macromonomers may be used as the macromonomers used when the graft polymer having an anchor moiety on the surface of the pigment is produced by radical polymerization. Macromonomer AA-6 (the terminal group of which is methacryloyl AS-6 (polystyrene having a terminal group of methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile having a terminal group of methacryloyl group), AB-6 (terminal group of a polymethyl methacrylate) Butyl acrylate), Flaccel FM5 (trade name, 5-mol equivalent of? -Caprolactone of 2-hydroxyethyl methacrylate) manufactured by Daicel Chemical Industries, Ltd., FA10L 10-molar equivalent of ε-caprolactone of hydroxyethyl), and polyester-based macromonomers described in JP-A-2-272009. Among these, polyester-based macromonomers having particularly good flexibility and good solvent resistance are particularly preferable from the viewpoints of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored curable composition using the pigment dispersion. Further, Based macromonomers such as the polyester-based macromonomers described in JP-A-272009 / 1999-2,2009.

As block type polymers having anchor sites on the pigment surface, block type polymers described in JP-A-2003-49110 and JP-A-2009-52010 are preferable.

Specific examples of the pigment dispersant usable in the present invention include commercially available products such as Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "by EFKA," EFKA 4047, 4050 to 4165 (high molecular weight unsaturated polycarboxylic acid) "by EFKA (High molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (high molecular weight polycarboxylic acid), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate) PB880, PB881 "manufactured by Ajinomoto Pine Techno Co., Ltd.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd.," Poly Flow No.50E, No.300 (Acrylic Copolymer) &quot;, Kusumoto Kasei (Polyetherester), DA-703-50, DA-705, DA-725 "manufactured by Kao Corporation," Demolon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid) RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L-18 (polymer polycarboxylic acid) "," Emulgen 920, 930, 935 (Polyoxyethylene nonylphenyl ether), &quot; acetamin 86 (stearylamine acetate) &quot;, Nissan Lubrizol &quot; Solspers 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (Graft polymer), NIKKOL T106 (polyoxyethylene sorbitan monooleate) manufactured by Nikko Chemical Co., Ltd., MYS-IEX (polyvinylpyrrolidone) (Polyoxyethylene monostearate), Hinoact T-8000E manufactured by Kawaken Fine Chemicals Co., Ltd., Ionet S-20 manufactured by Sanyo Chemical Industries, Ltd. .

These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymeric dispersant.

As the pigment dispersant of the present invention, an end-modified polymer having an anchor portion on the surface of the pigment, a graft-type polymer, and a block-type polymer may be used in combination with an alkali-soluble resin. Examples of the alkali-soluble resin include (meth) acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like, and acidic cellulose derivatives having a carboxylic acid group in the side chain, A resin obtained by modifying the polymer with an acid anhydride may be mentioned, but a (meth) acrylic acid copolymer is particularly preferable. The N-substituted maleimide monomer copolymer disclosed in JP-A-10-300922, the ether dimer copolymer disclosed in JP-A-2004-300204, the polymerizable group described in JP-A-7-319161 Is also preferable.

The content of the pigment dispersant in the polymerizable composition is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, and even more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the pigment as the coloring agent.

Specifically, when a polymeric dispersant is used, the amount of the polymer dispersant to be used is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the pigment.

When the pigment derivative is used in combination, the amount of the pigment derivative to be used is preferably in the range of 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the pigment Is particularly preferable.

When the pigment is used as the colorant in the polymerizable composition and the pigment dispersant is further used, the total content of the colorant and the dispersant is preferably 30% by mass or more to 90% by mass or more based on the total solid content constituting the polymerizable composition By mass or less, more preferably 40% by mass or more and 85% by mass or less, and still more preferably 50% by mass or more and 80% by mass or less.

< (b) Polymerizable compound >

The colored curable composition of the present invention can be preferably constituted by containing at least one kind of (b) polymerizable compound. The polymerizable compound is mainly included when the colored curable composition is constituted of a negative type.

In addition, the polymerizable compound may be contained in a positive system containing a naphthoquinone diazide compound together with a photopolymerization initiator described later, and in this case, the degree of curing of the formed pattern can be further promoted. Hereinafter, the polymerizable compound will be described.

The polymerizable compound is specifically selected from compounds having at least one terminal ethylenic unsaturated bond, preferably at least two terminal ethylenic unsaturated bonds. Such a group of compounds is well known in the industry, and can be used without particular limitation in the present invention. These may be, for example, any of chemical form such as monomer, prepolymer, that is, dimer, trimer and oligomer, or mixture thereof and (co) polymer thereof. The polymerizable compounds in the present invention may be used singly or in combination of two or more.

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, amides, ), Preferably an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound, and (co) polymers thereof. Further, an addition reaction product of monofunctional or polyfunctional isocyanates or epoxies of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group, an addition reaction product of a monofunctional or polyfunctional carboxyl A dehydration condensation reaction product of an acid is also preferably used. In addition, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of alcohols, amines and thiols with a monofunctional or multifunctional functional group, and a releasing substituent such as a halogen group or a tosyloxy group And amines, monofunctional or polyfunctional alcohols, amines, thiol substitution reaction products are also preferable. As another example, it is also possible to use a group of compounds in which the unsaturated carboxylic acid is substituted with an unsaturated phosphonic acid, styrene, vinyl ether, or the like.

As specific compounds of these compounds, compounds described in paragraphs 0095 to 0108 of Japanese Patent Laid-Open Publication No. 2009-288705 can be preferably used in the present invention.

Also, as the polymerizable compound, a compound having an ethylenic unsaturated group having a boiling point of 100 캜 or higher at atmospheric pressure and having at least one 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; (Meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isohexyl (meth) acrylate, pentaerythritol hexa (Meta) acrylate obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as propylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, , JP-A-51-37193, JP-A-48-64183, JP-A-49-43191, JP-A- Polyfunctional acrylates and methacrylates such as epoxy acrylates, reaction products of epoxy resin and (meth) acrylic acid, epoxy acrylates and the like, and mixtures thereof are disclosed in JP-B-52-30490 .

Also, as the compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 캜 or more at normal pressure, the compounds described in paragraphs [0254] to [0257] of JP-A No. 2008-292970 are also preferable.

In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) are also preferably used. In the formula, when T is an oxyalkylene group, the terminal of the carbon atom is bonded to R.

In the above general formula, n is 0 to 14, and m is 1 to 8. A plurality of R and T present in one molecule may be the same or different.

At least one of the plurality of R's in each of the radically polymerizable monomers represented by the general formulas (MO-1) to (MO-5) is -OC (═O) CH═CH ₂ or -OC (= O) C (CH ₃₎ represents a group represented by = CH _2.

Specific examples of the radically polymerizable monomers represented by the general formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of Japanese Patent Application Laid-Open No. 2007-269779 Can be preferably used.

Further, as the polymerizable monomer, it is preferable to contain a polyfunctional monomer having a caprolactone structure.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane, Caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol and trimethylol melamine with (meth) acrylic acid and epsilon -caprolactone, Acrylate. Among them, a polyfunctional monomer having a caprolactone structure represented by the following formula (i) is preferable.

(Wherein all of the six R's in the formula (i) are groups represented by the following formula (ii), or one to five of the six R's are groups represented by the following formula (ii) &Lt; / RTI &gt;

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

(In the formula (iii), R ¹ represents a hydrogen atom or a methyl group, and "*"

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., and DPCA-20 (in the formulas (i) to (iii) ii) a number of groups represented = 2, R ¹ are both a hydrogen atom), DPCA-30 (the same formula, m = 1, the number of groups represented by the formula (ii) = 3, R ¹ are both hydrogen atom a compound), DPCA-60 (the same formula, m = 1, formula (ii) the number of groups represented by = 6, R ¹ are both a hydrogen atom), m = 2 in the DPCA-120 (the same formula , The number of groups represented by the formula (ii) = 6, and R ¹ are all hydrogen atoms).

In the present invention, the polyfunctional monomers having a caprolactone structure may be used alone or in combination of two or more.

The content of the polymerizable compound in the colored curable composition of the present invention is preferably from 0.1% by mass to 90% by mass, more preferably from 1.0% by mass to 80% by mass, and still more preferably from 2.0% by mass to 70% by mass relative to the solid content in the colored curable composition. % By mass is particularly preferable.

In the tinting curable composition of the present invention, the content ratio of the pigment multimer to the polymerizable compound in the present invention (pigment multimer of the present invention: polymerizable compound) is 1: 2 to 20: 1 More preferably 1: 1 to 10: 1.

< (c) Photopolymerization initiator >

The colored curable composition of the present invention contains (c) a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as it can polymerize the above-mentioned polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, and cost.

Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl substituted coumarin compound, a ropin dimer, a benzophenone compound, an acetophenone compound And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs 0070 to 0077 of Japanese Patent Application Laid-Open No. 2004-295116. Of these, oxime compounds are preferable because of the fact that polymerization reaction is quick.

The oxime-based compound (hereinafter also referred to as &quot; oxime-based photopolymerization initiator &quot;) is not particularly limited, and examples thereof include compounds described in JP-A-2000-80068, WO02 / 100903A1, JP-A-2001-233842 Oxime compounds.

Specific examples thereof include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- -1,2-pentanedione, 2- (o-benzoyloxime) -1- [4- (phenylthio) (Phenylthio) phenyl] -1,2-octanedione, 2- (o-benzoyloxime) -1- -1- [4- (ethylphenylthio) phenyl] -1,2-butanedione, 2 (o-benzoyloxime) - (o-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- Benzoyl) -9H-carbazol-3-yl] ethanone, 1- (9-methyl- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol- (9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- -9H- Le carbazole-3-yl] ethanone, and the like. However, the present invention is not limited thereto.

(O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1 (phenylthio) phenyl] -1 O-acyl group such as 2-octanedione and 1- (o-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H- OXE-01, OXE-02 (manufactured by BASF), and the like can be given.

Further, in the present invention, compounds represented by the following formulas (E) and (F) are more preferable as the oxime compounds from the viewpoints of sensitivity, stability with time, and coloration upon post heating.

In the 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 to 5;

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

As A, an alkylene group substituted with an unsubstituted alkylene group, an alkyl group (e.g., methyl group, ethyl group, tert-butyl group or dodecyl group), an alkenyl group An aryl group (for example, a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a styryl group) substituted with an alkyl group, Is preferably an alkylene group substituted by an alkylene group.

As the Ar, a substituted or unsubstituted phenyl group is preferred in view of increasing the sensitivity and inhibiting coloration due to heating over time. In the case of a substituted phenyl group, as the substituent, for example, a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom is preferable.

X is preferably 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, a substituent which may have a substituent An alkoxy group, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, and an amino group which may have a substituent are preferable.

In the formulas (E) and (F), n is preferably an integer of 1 to 2.

Specific examples of the compounds represented by the formulas (E) and (F) are shown below, but the present invention is not limited thereto.

In addition to the above-mentioned photopolymerization initiator, other known photopolymerization initiators described in paragraph 0079 of Japanese Patent Application Laid-Open No. 2004-295116 may be used in the colored curable composition of the present invention.

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

The content (the total content in the case of two or more kinds) of the total solid content of the colored curable composition is preferably 3% by mass to 20% by mass, more preferably 4% by mass to 19% by mass %, And particularly preferably from 5% by mass to 18% by mass.

<(d) Organic solvent>

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

The organic solvent is not particularly limited insofar as it can satisfy the solubility of the coexisting components and the coating property when the composition is colored and curable, and is preferably selected in consideration of the solubility, coating ability, and safety of the binder .

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, butyl lactate , Ethyl lactate, and oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetic acid Ethyl, etc.)), 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate, ethyl 3-oxypropionate (specifically methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl ethoxypropionate and ethyl 3-ethoxypropionate), 2-oxypropionic acid alkyl esters ( Examples thereof include methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate (specifically, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Ethyl 2-ethoxypropionate), methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy- Methyl propionate and the like), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like .

Examples of the ethers include 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 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.

Examples of the ketone include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like.

As the aromatic hydrocarbons, for example, toluene, xylene and the like are preferably used.

These organic solvents are preferably mixed with two or more of them in terms of the solubility of each of the above-mentioned components and, in the case of containing an alkali-soluble binder, from the viewpoints of solubility and improvement in shape of the coated surface. In this case, particularly preferable examples thereof include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, Cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The content of the organic solvent in the colored curable composition is preferably such that the total solid content concentration in the composition is 10% by mass to 80% by mass, more preferably 15% by mass to 60% by mass.

(Other components)

The colored curable composition of the present invention may further contain other components such as an alkali soluble binder and a cross-linking agent in addition to the above-mentioned components in addition to the effects of the present invention.

- Alkali soluble binder -

The alkali-soluble binder is not particularly limited, except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability and the like.

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

Another preferred example of the binder in the present invention is a polymer containing, as a polymerization component, a structural unit derived from a compound represented by the following general formula (ED) (hereinafter, appropriately referred to as "ether dimer").

In the general formula (ED), R ²¹ and R ²² each independently represent a hydrogen atom or a hydrocarbon group of 1 to 25 carbon atoms which may have a substituent.

By using a binder containing a structural unit derived from an ether dimer, the polymerizable composition of the present invention has an advantage of being able to form a cured coating film having excellent transparency as well as heat resistance.

The hydrocarbon group having 1 to 25 carbon atoms, which may have a substituent represented by R ²¹ and R ²² in the general formula (ED) representing the ether dimer, is not particularly limited and includes, for example, methyl, ethyl, Straight or branched alkyl groups such as isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl and 2-ethylhexyl; An aryl group such as phenyl; Cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and the like; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a substituent of a primary or secondary carbon which is difficult to be desorbed by heat are preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include dimethyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2' - [oxybis (methylene)] bis- Di (isopropyl) -2,2 '- [oxybis (methylene)] propaneate, di (n-propyl) -2,2' - [oxybis Di (isobutyl) -2,2 '- [oxybis (2-methoxyphenyl) -2,2'- Methylene)] bis-2-propenoate, di (t-butyl) -2,2 '- [oxybis Di (stearyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 Bis (2-ethylhexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di Methoxyethyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, Bis (2-hydroxyethyl) bis-2-propenoate, dicyclohexyl-2,2 '- [oxybis Di (dicyclopentadienyl) -2,2 '- [oxybis (methylene)] - bis (2-propylphenyl) Di (tricyclodecanyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2' - [oxy Bis (methylene)] bis-2-propenoate, diadamantyl-2,2 '- [oxybis 2,2 '- [oxybis (methylene)] bis-2-propenoate, and the like.

Of these, especially preferred are dimethyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, diethyl- Bis [2-propenyl] hexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These structural units derived from an ether dimer may be contained in only one kind or two or more kinds in the binder.

The binder comprising a structural unit derived from a compound represented by the above general formula (ED) may be a copolymer containing a structural unit derived from a monomer other than the structural unit derived from a compound represented by the general formula (ED). Other monomers that can be used in combination are not particularly limited, and examples thereof include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (Meth) acrylate. Examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate , Polystyrene macromonomers, and polymethyl methacrylate macromonomers. Examples of the N-substituted maleimide monomers described in JP-A-10-300922 include N-phenylmaleimide, N- 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.

Examples of the alkali-soluble binder in the present invention include those obtained by adding an acid anhydride to a polymer having a hydroxyl group and the like, a polyhydroxystyrene resin, a polysiloxane resin, a poly (2-hydroxyethyl (meth) acrylate ), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful. The linear organic polymer may be a copolymer obtained by copolymerizing a monomer having hydrophilicity. Examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, di Vinyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, vinyltoluene, (Meth) acrylate, branched or straight chain propyl (meth) acrylate, branched or straight chain butyl (meth) acrylate, or phenoxy hydroxypropyl (meth) acrylate. Examples of the hydrophilic monomer include a tetrahydrofurfuryl group, a phosphoric acid group, a phosphoric acid ester group, a quaternary ammonium salt group, an ethyleneoxy chain, a propyleneoxy group, a group derived from a sulfonic acid group and a salt thereof, Monomers and the like are also useful.

Further, the alkali-soluble binder may have a polymerizable group in the side chain to improve the crosslinking efficiency, and for example, a polymer containing an allyl group, a (meth) acrylic group, an allyloxyalkyl group or the like in the side chain is also useful. Examples of the polymer containing the above polymerizable group include Diyanal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co. Ltd.), Viscot R-264, KS resist 106 (All manufactured by Osaka Yuki Kagaku Kogyo K.K.), Cychroma P series, PLACCEL CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by DAICEL YUSHIBA CORPORATION) . Further, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured coating.

Among these various alkali-soluble binders, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin and an acryl / acrylamide copolymer resin are preferable from the viewpoint of heat resistance, and from the viewpoint of development control, Amide type resin, and acrylic / acrylamide copolymer resin are preferable.

Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, etc., and Photomer 6173, KS Resist- Cyclom P series and the like are preferable.

As the alkali-soluble binder, a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 x 10 ⁵ is preferable from the viewpoints of developability and liquid viscosity, and a polymer of 2000 to 1 x 10 ⁵ is more preferable , And particularly preferably from 5000 to 5 x 10 &lt; ^{4 &} gt ;.

- Cross-linking agent -

The hardness of the colored cured film obtained by curing the colored curable composition by using a crosslinking agent in addition to the colored curable composition of the present invention may be further increased.

The crosslinking agent is not particularly limited as long as it can perform film curing by a crosslinking reaction. Examples of the crosslinking agent include (a) an epoxy resin, (b) at least one substituent selected from methylol group, alkoxymethyl group and acyloxymethyl group (C) a phenol compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, a naphthol compound or a hydroxyanthracene Compounds. Among them, a polyfunctional epoxy resin is preferable.

Specific examples of the crosslinking agent and the like can be found in paragraphs 0134 to 0147 of Japanese Patent Application Laid-Open No. 2004-295116.

- Polymerization inhibitor -

In the colored curable composition of the present invention, it is preferable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during storage of the colored curable composition.

Examples of the polymerization inhibitor usable in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine cerium salt.

The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition.

-Surfactants-

A surfactant may be added to the colored curable composition of the present invention. As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

In particular, by containing a fluorine-based surfactant, it is possible to further improve the liquid properties (in particular, fluidity) of a coating liquid, thereby further improving the uniformity of coating thickness and the liquid saving.

That is, in the polymerizable composition containing the fluorine-containing surfactant, the wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, and the coatability to the surface to be coated is improved. Therefore, even in the case of forming a thin film having a thickness of several mu m to several tens of mu m at a small liquid amount, it is effective in that a film having a uniform thickness with a small thickness deviation can be formed more preferably.

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

Examples of the fluorochemical surfactant include Megapac 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 (Manufactured by Sumitomo 3M Ltd.), Surflon S-382, and SC-101 (manufactured by Sumitomo 3M Ltd.), F554, F780, and F781 (manufactured by DIC Corporation), Fluorad FC430, , SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH-40 (manufactured by Asahi Garas Co., Ltd.) .

Specific examples of the cationic surfactant include phthalocyanine derivatives (commercially available product EFKA-745 (Morishita Chemical Co., Ltd.)), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid- 75, No. 90, No. 95 (manufactured by Kyoeisha Yushikagaku Kogyo Co., Ltd.), and W001 (manufactured by YUSHACHA CO., LTD.).

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF L100, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 etc.) and Solpus 20000 (manufactured by Zeneca).

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by YUCHO Co., Ltd.) and the like

Examples of silicone surfactants include TORAY Silicone DC3PA, Dong SH7PA, Dong DC11PA, Dong SH21PA, Dong SH28PA, Dong SH29PA, Dong SH30PA, TSF-4440 "," TSF-444 (4) (5) (6) (7) 6 "," TSF-4400 " -4460 &quot;, &quot; TSF-4452 &quot;, Shinetsu Silicones KP341, BYK307 BYK323, BYK330 and the like.

Two or more kinds of surfactants may be combined.

- Other additives -

Various additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent and the like may be added to the color-curable composition, if necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of Japanese Patent Application Laid-Open No. 2004-295116.

The color-curable composition of the present invention may contain a sensitizer or light stabilizer described in paragraph 0078 of Japanese Patent Application Laid-Open No. 2004-295116, or a thermal polymerization inhibitor described in paragraph 0081 of the same publication.

In order to promote the alkali solubility of the non-exposed region and further improve the developability of the colored curable composition, it is preferable to add an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less, .

Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid and caprylic acid; There may be mentioned oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, , Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and canononic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemellitic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melotropic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydro atropic acid, hydroxycarboxylic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, cumalic acid and umberic acid .

[Process for preparing colored curable composition]

The colored curable composition of the present invention is prepared by mixing the above-mentioned components.

Further, in the preparation of the colored curable composition, each component constituting the colored curable composition may be blended at one time, or each component may be dissolved and dispersed in a solvent and then blended sequentially. In addition, the order of injection and the working conditions at the time of compounding are not particularly limited. For example, the composition may be prepared by dissolving or dispersing the entire components in a solvent at the same time. If necessary, the components may be appropriately mixed into two or more solutions and dispersions, and they are mixed at the time of use Maybe.

The color-curable composition prepared as described above is preferably filtered through a filter having a pore diameter of 0.01 to 3.0 m, more preferably a pore diameter of about 0.05 to 0.5 m, have.

The colored curable composition of the present invention is excellent in storage stability and can form a colored cured film having excellent light fastness. Therefore, the color curable composition of the present invention can be used as a color filter (liquid crystal display device (LCD) , And also for the production of printing ink, ink-jet ink, and paint. In particular, it can be preferably used for forming a colored pixel for a solid-state imaging element such as a CCD and a CMOS.

«Color filter and its manufacturing method»

Next, a method of manufacturing a color filter (a method of manufacturing a color filter of the present invention) using the colored curable composition of the present invention will be described.

In the method for producing a color filter of the present invention, the above-mentioned colored curable composition of the present invention is applied on a support by a coating method such as spin coating, soft coating or roll coating to form a colored curable composition layer, Pre-curing (pre-baking) is performed as necessary to dry the colored curable composition (coating step).

Examples of the support used in the method for producing a color filter of the present invention include alkali-free glass, soda glass, borosilicate glass (Pyrex (registered trademark) glass), quartz glass, and a transparent conductive film A photoelectric conversion element substrate used for a solid-state imaging element such as a CCD or a CMOS, and the like. These substrates may be formed with black stripes for isolating each pixel. On the support, a primer layer may be formed on the support in order to improve adhesion with the upper layer, prevent diffusion of the material, or planarize the surface.

When the colored curable composition is spin-coated on the support, an appropriate organic solvent is added dropwise prior to the dropwise addition of the colored curable composition in order to reduce the drop amount of the solution, and the colored curable composition can be well fused to the support.

In the step of applying the colored curable composition of the present invention, even when a colored curable composition is adhered to, for example, a nozzle of a coating device discharging portion, a pipe portion of a coating device, or a coating device, Can be removed. In this case, it is preferable to use the above-mentioned solvent as a cleaning liquid for the solvent included in the color-curable composition of the present invention in order to carry out washing and cleaning more efficiently.

In addition, Japanese Patent Application Laid-Open Nos. 7-128867, 7-146562, 8-278637, 2000-273370, 2006-85140, The cleaning liquids described in JP-A-2006-291191, JP-A-2007-2101, JP-A-2007-2102 and JP-A-2007-281523 also disclose cleaning liquids for cleaning and removing the color- It can be preferably used as a cleaning liquid.

As the cleaning liquid, it is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether.

These solvents used as a cleaning liquid may be used alone or in combination of two or more kinds.

When mixing two or more kinds of solvents, a mixed solvent comprising a mixture of a solvent having a hydroxyl group and a solvent having no hydroxyl group is preferable. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10 and more preferably from 20/80 to 80/20. As the mixed solvent, it is particularly preferable to use a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) at a ratio of 60/40.

In order to improve the permeability of the cleaning liquid to the colored curable composition, the above-described surfactant may be added to the cleaning liquid as a surfactant that the colored photosensitive composition can contain.

As the prebaking condition, a condition of heating at 70 to 130 캜 for about 0.5 to 15 minutes using a hot plate or an oven can be mentioned.

The thickness of the colored curable composition layer formed from the colored curable composition is appropriately selected according to the purpose, but it is generally preferably from 0.2 to 5.0 m, more preferably from 0.3 to 2.5 m, Most preferably 1.5 m. The thickness of the layer of the color-curable composition referred to herein is the film thickness after pre-baking.

Subsequently, in the production method of the color filter of the present invention, the layer of the colored curable composition formed on the support is exposed through a mask (exposure step).

The light or radiation usable in this exposure is preferably g-line, h-line, i-line, KrF light, or ArF light, particularly i-line. When the i-line is used as the irradiation light, it is preferable that the irradiation is performed at an exposure amount of 100 mJ / cm 2 to 10000 mJ / cm 2.

Further, the exposed colored curable composition layer can be heated at 70 캜 to 180 캜 for 0.5 minute to 15 minutes using a hot plate or an oven before the next development processing.

The exposure can be performed while flowing nitrogen gas into the chamber in order to suppress oxidation and discoloration of the colorant in the colored curable composition layer.

Subsequently, the layer of the colored curable composition after exposure is developed with a developing solution (developing step). Thus, a colored pattern (resist pattern) of a negative or positive type can be formed.

The developing solution may be a combination of various organic solvents, or a combination of various organic solvents such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, meta-sodium (meth) acrylate and the like, as long as it dissolves the unhardened portion (unexposed portion) of the colored curable composition layer and does not dissolve the cured portion Diazabicyclo- [5,4-dioxabicyclo [4.4.1] octane-1-carboxylate, sodium carbonate, sodium silicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammoniumhydroxide, tetraethylammoniumhydroxide, choline, pyrrole, piperidine, , 0] -7-undecene, and the like can be used.

When the developer is an alkaline aqueous solution, it is preferable to adjust the alkali concentration to preferably pH 11 to 13, more preferably pH 11.5 to 12.5. In particular, an alkaline aqueous solution in which tetraethylammonium hydroxide is adjusted to have 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 developer.

The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 to 40 캜, more preferably 23 캜.

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

Further, after development using an alkaline aqueous solution, it is preferable to rinse with water. The rinse process can be appropriately selected in accordance with the purpose. However, the rinse process can be performed by supplying pure water from the spray nozzle to the showerhead from above the rotation center while rotating the support at a rotational speed of 10 rpm to 500 rpm.

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

- UV irradiation process -

The ultraviolet light irradiation step irradiates ultraviolet light (UV light) with an irradiation light amount [mJ / cm 2] at least 10 times the exposure amount [mJ / cm 2] in the exposure processing before development to the pattern after the development processing in the above- . Between the developing treatment in the pattern forming step and the heat treatment to be described later, the post-development pattern (colored curable composition) is irradiated with UV light for a predetermined time to effectively prevent color conversion when heated later, and light resistance is improved.

Examples of the light source for irradiating UV light include ultrahigh pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, and DEEP UV lamps. In particular, it is possible to irradiate light having wavelengths of 275 nm or shorter and ultraviolet light having a wavelength of 275 nm or less in irradiation intensity [mW / cm 2] in the ultraviolet light irradiated with 5% or more of the total irradiation intensity of the entire wavelength light in ultraviolet light . By setting the irradiation intensity of the wavelength light of 275 nm or less in the ultraviolet light to 5% 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 improved more effectively. In this respect, it is preferable to use a light source different from a light source such as an i-line used for exposure in the pattern formation step, specifically, a high-pressure mercury lamp or a low-pressure mercury lamp. Of these, for the same reason as described above, the integrated illumination intensity of the entire wavelength light in ultraviolet light is preferably 7% or more. The upper limit of the irradiation intensity of the wavelength light of 275 nm or less is preferably 25% or less.

In addition, when the integrated irradiation illuminance is a curve in which the ordinate axis is the illuminance (the radiant energy passing through the unit area per unit time in unit time) per spectral wavelength and the abscissa is the wavelength [nm] of the light, (Area) of the illuminance of each wavelength light included in the light source.

The irradiation of UV light is preferably performed at an irradiation light amount [mJ / cm &lt; 2 &gt;] of 10 times or more the exposure amount at the time of exposure in the pattern formation step. If the amount of light irradiated in this step is less than 10 times, color conversion between colored pixels or between upper and lower layers can not be prevented, and light resistance may be deteriorated.

Among them, the amount of UV light to be irradiated is preferably 12 times or more and 200 times or less, more preferably 15 times or more and 100 times or less the exposure amount in exposure in the pattern forming step.

In this case, it is preferable that the integrated irradiation illuminance in the ultraviolet light to be irradiated is 200 mW / cm 2 or more. When the integrated irradiation illuminance is 200 mW / cm 2 or more, it is possible to more effectively enhance 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. Among them, 250 to 2000 mW / cm2 is preferable, and 300 to 1000 mW / cm2 is more preferable.

Post-heating is preferably carried out at 100 ° C to 300 ° C, more preferably 150 ° C to 250 ° C, using a hot plate or an oven. The post-heating time is preferably 30 seconds to 30000 seconds, more preferably 60 seconds to 1000 seconds.

On the other hand, the post-exposure can be performed by g line, h line, i line, KrF, ArF, UV light, electron beam, X line or the like, but g line, h line, i line and UV light are preferable, . When UV light irradiation (UV curing) is carried out, it is preferably carried out at a low temperature of 20 ° C or more and 50 ° C or less (preferably 25 ° C or more and 40 ° C or less). The wavelength of the UV light preferably includes a wavelength in the range of 200 nm to 300 nm. As the light source, for example, a high-pressure mercury lamp or a low-pressure mercury lamp can be used. The irradiation time is 10 seconds to 180 seconds, preferably 20 seconds to 120 seconds, and more preferably 30 seconds to 60 seconds.

Either of the post exposure and the post heating may be performed first, but it is preferable to perform the post exposure before the post heating. This is because accelerating the curing by post-exposure inhibits thermal deformation of the pattern seen in the post-heating process or deformation of the shape due to pulling down.

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

In the production of a color filter having pixels of a plurality of colors, the coating step, the exposing step, and the developing step (curing step if necessary) described above may be repeated in accordance with the desired number of colors.

The color filter (color filter of the present invention) obtained by the method for producing a color filter of the present invention is excellent in light fastness because it uses the color curable composition of the present invention.

Therefore, the color filter of the present invention can be used for a solid-state image pickup device such as a liquid crystal display device, a CCD image sensor, a CMOS image sensor, and the like, and a camera system using the solid-state image pickup device. Among them, The use of a solid-state image pickup device in which a good rectangular cross-sectional profile is required, particularly for use in high-resolution CCD devices and CMOS devices exceeding 1 million pixels.

<Solid-state image sensor>

The solid-state image pickup device of the present invention includes the color filter of the present invention. The color filter of the present invention has a high light resistance, and a solid-state image pickup device having the color filter can obtain good color reproducibility.

The configuration of the solid-state image pickup device is not particularly limited as long as it includes the color filter of the present invention and functions as a solid-state image pickup device. For example, the following configuration can be given.

That is, a plurality of photodiodes constituting a light receiving area of a CCD image sensor (solid-state image pickup device) and a transfer electrode made of polysilicon or the like are provided on a support, a color filter of the present invention is provided thereon, Respectively.

The camera system having the color filter of the present invention is provided with a camera lens, a cover glass coated with a dichroic coating on the IR cut film, a microlens, etc. from the viewpoint of the light discoloration property of the color material, It is preferable to absorb a part or all of the UV light. In addition, as the structure of the camera system, it is preferable that the structure of the camera system is such that the oxygen permeability to the color filter is reduced in order to suppress oxidation and discoloration of the color material. For example, a part or all of the camera system is sealed with nitrogen gas desirable.

<Liquid crystal display device, organic EL display device>

The color filter of the present invention is used for a liquid crystal display device and a color filter for an 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 with good display image tone and excellent display characteristics.

The definition of the display device and the details of each display device are described in detail, for example, in "Electronic Display Device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 Issued)", "Display Device (Ibukisumi Architect, Published in 1989 "). The liquid crystal display device is described in, for example, &quot; Next Generation Liquid Crystal Display Technology (edited by Utsuda Tatsuo, published by Sakai High School, 1994). The liquid crystal display device and the organic EL display device to which the present invention can be applied are not particularly limited. For example, the liquid crystal display device and the organic EL display device described in the &quot; next generation liquid crystal display technology &quot; Can be applied.

The color filter of the present invention may be used in a color TFT type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, &quot; Color TFT liquid crystal display (published by KITOROZSHO, 1996). &Quot; The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as an IPS or a pixel division system such as an MVA or an STN, TN, VA, OCS, FFS and R-OCB .

In addition, the color filter of the present invention can also be provided in a bright and high-definition color-filter on array (COA) system. In the COA type liquid crystal display device, the required characteristics for the color filter layer may be required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the above-mentioned usual required characteristics. In the color filter of the present invention, since a dye multimer having excellent color is used, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided because color tone such as color purity is excellent. Further, a resin film may be formed on the color filter layer in order to satisfy the requirement of low dielectric constant.

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

The liquid crystal display of the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer r, and a viewing angle compensation film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members. These members are described in, for example, "The market of materials and chemicals around the LCD display (Shimashita Shimasho Co., Ltd., 1994)", "2003 Current situation of liquid crystal related market and the future prospect (the second one) (Omote Yoshikichi (Issued by Fujiki Kenkaku Co., Ltd., 2003).

The backlight is described in the SID meeting Digest 1380 (2005) (A.Konno et al), in the monthly display December 2005, pages 18-24 (Yamazaki Shimaya), pp. 25-30 (Yagi Takaaki) .

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode fluorescent lamp. In addition, a red light source (RGB-LED) It is possible to provide a liquid crystal display device having high luminance, high color purity, and good color reproducibility.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless the present invention exceeds the conventional limit. Unless otherwise stated, &quot; part &quot; and &quot;% &quot; are based on mass.

[Example 1-1]

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

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

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

· Cyclohexanone (hereinafter referred to as CyH) ... 52.60 part

·bookbinder… 30.50 parts

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

· Dipentaerythritol hexaacrylate ... 10.20 part

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

· Fluorine-based surfactant (F-475 made by DIC Corporation) ... 0.80 part

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

(2) Preparation of a glass substrate on which a primer layer was formed

The glass substrate (Corning 1737) was subjected to ultrasonic cleaning with 0.5% NaOH water, followed by washing with water and dehydration baking (200 ° C / 20 minutes). Subsequently, the resist solution A obtained in the above (1) was applied to a cleaned glass substrate using a spin coater so as to have a thickness of 2 탆 after drying, and dried by heating at 220 캜 for one hour to prepare a glass substrate did.

(3) Preparation of colored curable composition

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

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

That is, C.I. A mixed solution composed of 11.8 parts of Pigment Blue 15: 6 (average particle diameter 55 nm), 5.9 parts of pigment dispersant BYK-161 (manufactured by BYK) and 82.3 parts of PGMEA was mixed and dispersed for 3 hours by a bead mill (zirconia beads 0.3 mm in diameter) To prepare a pigment dispersion. Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 (manufactured by Nippon Bai Co., Ltd.) equipped with a pressure reducing mechanism. This dispersion treatment was repeated ten times to obtain a pigment dispersion (CI Pigment Blue 15: 6 dispersion). The average primary particle diameter of the pigment for the obtained pigment dispersion was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150, manufactured by Nikkiso) to be 24 nm.

(3-2) Preparation of colored curable composition

The following components were mixed to obtain a colored curable composition.

· Solvent: CyH ... 1.133 part

· Alkali-soluble resin: benzyl methacrylate / 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.) 0.225 part

· Surfactant: Sol Spurs 20000 (1% cyclohexane solution, manufactured by Zeneca) ... 0.125 part

· Oxime-based photopolymerization initiator (compound of the following structure) 0.087 part

· Colorant multimer (Exemplified compound S-1) 0.183 part

· Pigment Blue 15: 6 dispersion ... 2.418 part

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

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

(4) Exposure / development (image formation) of the tinted curable composition [

The colored curable composition obtained in the above (3) was applied to a primer layer of a glass substrate on which the primer layer obtained in the above (2) was formed, using a spin coater so that the film thickness after drying became 0.6 탆, and prebaked at 100 캜 for 120 seconds did.

Subsequently, an exposure apparatus UX3100-SR (manufactured by Ushio DENKI CO., LTD.) Was used and the coating film was irradiated with an exposure amount of 200 mJ / cm2 through a mask having a wavelength of 365 nm and a line width of 2 m. After exposure, development was carried out at 25 占 폚 for 40 seconds using Developer CD-2000 (manufactured by Fuji Film Electronics Matrix Co., Ltd.). Thereafter, after rinsing with running water for 30 seconds, spray drying was performed. Thereafter, post baking was performed at 200 DEG C for 15 minutes.

(5) Evaluation

The heat resistance, solvent resistance, and light resistance of a coated film applied on a glass substrate using the tinted 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 캜 so as to be in contact with the substrate surface, and heated for one hour, and then heated with a color meter MCPD-1000 (manufactured by Otsuka The color difference (? E ^* ab value) between before and after was measured and used as an index for evaluating the fastness to heat, and evaluated according to the following criteria. The value of? E ^* ab indicates that heat resistance is good when the value is smaller. The value of? E ^* ab is a value obtained from the following color difference formula by the spatial colorimetry system of CIE 1976 (L ^* , a ^* , b ^* ) (Japanese Society of Color Science Handbook, New Color Science Handbook (1986) p.266) .

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

-Criteria-

?:? E ^* ab value <3

0: 3?? E ^* ab value <5

?: 5?? E ^* ab value? 15

×: ΔE ^* ab value> 15

[Solubility]

The spectra of the various coating films after post-baking obtained in (4) above were measured (spectroscopic A). The resist solution A obtained in the above (1) was applied to the coating film so as to have a thickness of 1 탆 and pre-baked. Then, 23 탆 of the coating film was formed using CD-2000 (manufactured by FUJIFILM ELECTRONICS MATERIALS CO. Deg.] C for 120 seconds, and the spectroscopic measurement was again performed (spectral B). The dye remaining ratio (%) was calculated from the ratio of the spectra A and B, and this was used as an index for evaluating the solvent resistance. This value indicates that the closer to 100% the better the solvent resistance.

-Criteria-

?: Residual dye ratio> 90%

?: 70%? Dye remaining ratio? 90%

X: dye remaining ratio < 70%

[Light Resistance]

The spectra of the various coating films after post-baking obtained in (4) above were measured (spectroscopic A). The coating film was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2,000,000 lux · h). The color difference (? E ^* ab value) of the coating film before and after the xenon lamp irradiation was measured and used as an index of the light resistance. The smaller the value of? E ^* ab is, the better the light resistance is, and the judgment criteria are as follows.

-Criteria-

?:? E ^* ab value <3

?: 3?? E ^* ab value <5

?: 5?? E ^* ab value? 15

×: ΔE ^* ab value> 15

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

A pattern was prepared in the same manner as in Example 1-1 except that Example Compound S-1 was changed to the colorant described in the following Table 2 in the preparation of the (3) colored curable composition of Example 1-1 And the same evaluation was made. The evaluation results are shown in Table 2. The structures of the comparative dye 1 and the comparative dye 2 (C.I. Acid Red 87) in Table 2 are shown below.

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

Coloring curable compositions used in Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-2 were used to prepare color filters in the following procedure, and in 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 filter -

The colored curable compositions used in Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-2 were used on a glass substrate on which the primer layer (2) prepared in Example 1-1 was formed, Using a spin coater so as to have a film thickness of 1 mu m and prebaked at 100 DEG C for 120 seconds to form a colored film. The coloring film was exposed to an exposure amount of 200 [mJ / cm 2] by a i-line stepper (FPA-3000i5 + manufactured by Canon) through a mask pattern in which square pixels of 7.0 탆 were arranged in a region of 4 mm x 3 mm on the substrate And then exposed at 1200 mW / cm 2 (integral irradiation illuminance). After the exposure, paddle development was performed at 23 DEG C for 60 seconds using a developing solution (CD-2000, 60%, manufactured by Fuji Film Electronics Matrix Co., Ltd.) to form a pattern. Then rinsed with running water for 20 seconds, and spray dried. Thereafter, an ultraviolet ray of 10000 [mJ / cm 2] was irradiated onto the entire glass substrate on which the pattern was formed as the ultraviolet irradiation process after the development process, using a high-pressure mercury lamp (UMA-802-HC552FFAL). After irradiation, post baking treatment was performed on a hot plate at 220 占 폚 for 300 seconds to form a colored pattern on the glass substrate. The wavelength light of 275 nm or less included in the irradiation light from the high-pressure mercury lamp is 10%.

- Color conversion evaluation -

A CT-2000L solution (an undercoating agent, manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.) Was applied on the colored pattern formation side of the color filter prepared as described above so as to have a dry film thickness of 1 mu m, After forming a transparent film, heat treatment was performed at 200 캜 for 5 minutes. After completion of the heating, the absorbance of the transparent film adjacent to the colored pattern was measured with a brown spectrophotometer (LCF-1500M manufactured by Otsuka Denshi Co., Ltd.). The ratio [%] of the absorbance of the obtained transparent film was calculated with respect to the absorbance of the coloring pattern measured before heating, and used as an index for evaluating the color conversion.

-Criteria-

Color conversion to adjacent pixels (%)

◎: Color conversion to adjacent pixels <1%

?: 1% <color conversion to adjacent pixels? 10%

?: 10%? Color conversion to adjacent pixels? 30%

×: Color conversion to adjacent pixels> 30%

As shown in Tables 2 and 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. In Examples 2-1 to 2-17 using the dye multimer of the present invention, color conversion to an adjacent pattern was suppressed.

Further, the same results as in Example 1-1 were obtained when the photopolymerization initiator of Example 1-1 was changed to the compounds OXE-01 and OXE-02 of the following structures, respectively, and the oxime-based initiator It was found that the used color-curable composition had good heat resistance, solvent resistance and light resistance.

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

Claims (16)

A dye multimer having a carboxyl group and a weight average molecular weight of 5,000 to 30,000 as a partial structure of a pigment part and having a pigment skeleton derived from a xanthene compound represented by the following formula (M)

Wherein R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a monovalent substituent, R ⁵ independently represents a monovalent substituent, m is an integer from 0 to 5, Represents an integer.]
Wherein the dye multimer is a multimer containing at least one of the structural units represented by the following general formulas (B) and (C), or a pigment multimer represented by the following general formula (D) In the case where the polymer is a large amount containing a constitutional unit represented by the general formula (C), L ³ in the general formula (C) has a carboxyl group and the dye skeleton derived from the xanthene compound represented by the general formula (M) Characterized in that it does not contain a pigment.

General formula (B) of X ² represents a connecting group formed by a polymerization, L ² is either a single bond, -C (= O) -, -O-, -NR- (R represents a hydrogen atom, an alkyl group, an aryl Or a heterocyclic group), -SO ₂ -, a substituted or unsubstituted straight-chain alkylene group having 1 to 30 carbon atoms, or a divalent linking group formed by connecting two or more thereof, A represents an ion- And Dye represents a dye residue capable of ionic bonding with A by removing one hydrogen atom from the above general formula (M).
A is selected from the group consisting of:

(Wherein * represents a position bonding with L ^2, and R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.)]

[Formula (C) of the L ³ represents a divalent linking group, if present, the plural L ³ is the structure of the L ³ is gatahdo or different. Dye represents a pigment residue in which two arbitrary hydrogen atoms have been removed from the above general formula (M). and n3 represents an integer of 1 to 4.]

Wherein L ⁴ represents a linking group of an n4 valent, n4 represents an integer of 2 to 100, and each of a plurality of Dye's independently represents a dye residue obtained by removing one arbitrary hydrogen atom from the general formula (M) .] The method according to claim 1,
Wherein the dye multimer is a multimer having a structural unit represented by the general formula (B), or a multimer having a large amount represented by the general formula (D). The method according to claim 1 or 2,
L ³ in the general formula (C) is selected from the group consisting of divalent linking groups having the following structure.

The method according to claim 1 or 2,
And the dye multimer does not contain silicon. delete delete The method according to claim 1 or 2,
In the general formula (C), L ³ includes any one of -NR- (R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group), -C (= O) - or -O- Of the pigment. The method according to claim 1 or 2,
L ⁴ in the general formula (D) includes -S-. As a dye multimer containing a pigment skeleton derived from a xanthene compound represented by the following formula (M) as a partial structure of a dye part,

Wherein R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a monovalent substituent, R ⁵ independently represents a monovalent substituent, m is an integer from 0 to 5, Represents an integer.]
Wherein the dye multimer is a multimer containing at least one of the structural units represented by the following general formulas (B) and (C), or a pigment multimer represented by the following general formula (D) In the case of a large amount of the constituent unit containing the structural unit represented by the general formula (C), the dye skeleton derived from the xanthene compound represented by the general formula (M) has no carboxyl group,
The dye multimer represented by the general formula (D) has an alkali-soluble group.

General formula (B) of X ² represents a connecting group formed by a polymerization, L ² is either a single bond, -C (= O) -, -O-, -NR- (R represents a hydrogen atom, an alkyl group, an aryl Or a heterocyclic group), -SO ₂ -, a substituted or unsubstituted straight-chain alkylene group having 1 to 30 carbon atoms, or a divalent linking group formed by connecting two or more thereof, A represents an ion- And Dye represents a dye residue capable of ionic bonding with A by removing one hydrogen atom from the above general formula (M).
A is selected from the group consisting of:

(Wherein * represents a position bonding with L ^2, and R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.)]

[Formula (C) of the L ³ represents a divalent linking group, if present, the plural L ³ is the structure of the L ³ is gatahdo or different. Dye represents a pigment residue in which two arbitrary hydrogen atoms have been removed from the above general formula (M). and n3 represents an integer of 1 to 4.]

Wherein L ⁴ represents a linking group of an n4 valent, n4 represents an integer of 2 to 100, and each of a plurality of Dye's independently represents a dye residue obtained by removing one arbitrary hydrogen atom from the general formula (M) .] The method of claim 9,
Wherein the dye multimer is a multimer having a structural unit represented by the general formula (B), or a multimer having a large amount represented by the general formula (D). The method according to claim 9 or 10,
L ³ in the general formula (C) is selected from the group consisting of divalent linking groups having the following structure.

The method according to claim 9 or 10,
And the dye multimer does not contain silicon. delete delete The method according to claim 9 or 10,
In the general formula (C), L ³ includes any one of -NR- (R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group), -C (= O) - or -O- Of the pigment. The method according to claim 9 or 10,
L ⁴ in the general formula (D) includes -S-.