KR20140001731A - Colored resin composition for use in color filter, color filter, display device, and solid-state imaging element - Google Patents

Abstract

상기 식에서, R₂ 및 R₁₅∼R₁₈은 각각 독립적으로 수소원자, C1-C30의 알킬기, 페닐기 또는 벤질기를 나타내고, R₁ 및 R₃∼R₁₄는 각각 독립적으로 수소원자, 할로겐 원자, C1-C12의 알킬기를 나타내며, X^-는 할로게노알킬설포닐이미드아니온, 할로게노알킬설포닐메티드아니온, 또는 할로게노알킬설포네이트아니온을 나타내고, 각각의 할로게노알킬기는 각각 독립적으로, 3∼6개의 할로겐 원자로 치환된 C1-C10알킬기이다.The present invention relates to a color filter colored resin composition containing a colorant compound of the following formula (1), a binder resin, a solvent, a polymerization initiator, and a curing agent, a color filter having the cured product, and the colored resin composition contains a metal phthalocyanine pigment. It is possible to provide a color filter pixel having good storage stability and excellent color characteristics and excellent heat resistance.

In the above formula, R ₂ and R ₁₅ to R ₁₈ each independently represent a hydrogen atom, an alkyl group of C1-C30, a phenyl group or a benzyl group, and R ₁ and R ₃ to R ₁₄ each independently represent a hydrogen atom, a halogen atom or C1- C12 represents an alkyl group, X ^- represents a halogenoalkylsulfonylimide anion, a halogenoalkylsulfonylmethed anion, or a halogenoalkylsulfonate anion, and each halogenoalkyl group is each independently 3 C1-C10 alkyl group substituted with -6 halogen atoms.

Description

Colored resin composition for color filter, color filter, display device and solid-state image sensor {COLORED RESIN COMPOSITION FOR USE IN COLOR FILTER, COLOR FILTER, DISPLAY DEVICE, AND SOLID-STATE IMAGING ELEMENT}

The present invention relates to a colored resin composition for forming a blue pixel, a color filter formed using the same, and an electronic display device such as a liquid crystal display, an imaging device (CCD, CMOS), an organic EL display, and the like formed using the color filter. .

Color filters are required for colorizing liquid crystal display devices such as liquid crystal displays (LCDs) such as laptops, liquid crystal televisions, mobile phones, and imaging devices (CCD, CMOS) used as input devices such as digital cameras and color copying machines. . As a method of manufacturing the color filter used for these liquid crystal display devices and a solid-state image sensor, there exist a dyeing method, an electrodeposition method, the printing method, the pigment dispersion method, etc. In recent years, pigment dispersion method has become mainstream. As a patterning method, the photolithographic method is typical and the color filter is formed using the mixture of the photosensitive resin composition and a pigment dispersion. Recently, a method of applying a coloring ink directly onto a substrate by an inkjet printer without passing through a mask and forming a color filter is also performed.

The improvement of color purity, color, brightness and contrast, which are characteristics required for color filters, is particularly important. Since the brightness is improved, the amount of light of the backlight can be suppressed and the power consumption can be lowered, which is an environmentally necessary technique. In order to improve the color purity of the color filter, it is necessary to increase the content of the colored pigment or to select a pigment having a better spectral waveform. On the other hand, in order to improve the brightness, it is necessary to increase the transmittance, and conversely, the pigment concentration must be reduced or the film thickness must be made thin. In order to make these opposite characteristics compatible, the method of particle | grains of a pigment is performed, but there exists a limit in tolerance and dispersion stability, and it is the present state that compatibility with tolerance is not aimed at even if brightness is improved.

Examination of the color filter using dye as an approach for solving these problems is progressing. The use of dyes has the merit that the contrast can be improved because light scattering can be suppressed in terms of both color purity and brightness that can not be achieved with pigments, or because they are not particles. However, in the case of the display object which requires long-term reliability, such as a television, light resistance and heat resistance are required, and especially blue dyes are much less resistant than pigment. For example, the following patent documents 1 and 2 report on the color filter using a triphenylmethane type compound. However, the triphenylmethane compound described therein is significantly inferior in light resistance and heat resistance and is not a practical level. However, although it is well-known (patent document 3) that a phthalocyanine-type dye is excellent in tolerance, since the color characteristic is not blue but generally red cyanide, a clear blue pixel cannot be formed. Although the color filter requires the colored resin composition which is a clear blue pixel and is highly reliable, and has the color material with high tolerance, it is a present state that it is almost not put to practical use. Therefore, there is a demand for a high quality color filter having a vivid color characteristic and excellent resistance as a next generation.

Japanese Laid-Open Patent Publication H08-94826 Japanese Unexamined Patent Publication No. 2002-14222 Japanese Patent Laid-Open No. S60-249102 Japanese Patent Laid-Open No. S63-172772

An object of the present invention is to provide a color filter having a vivid color characteristic and excellent in heat resistance and the like.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, it discovered that the said subject can be solved by using the colored resin composition containing a specific color material compound for the pixel of a color filter, and completed this invention. It was.

That is, this invention relates to following (1)-(12).

(1) The colored resin composition for color filters containing the color material compound of the following formula (1), binder resin, a solvent, a polymerization initiator, and a hardening | curing agent:

In the above formula, R ₂ and R ₁₅ to R ₁₈ each independently represent a hydrogen atom, an alkyl group of C1-C30, a phenyl group or a benzyl group, and R ₁ and R ₃ to R ₁₄ each independently represent a hydrogen atom, a halogen atom or C1- An alkyl group of C12 is shown. X ⁻ represents a halogenoalkylsulfonylimide anion, halogenoalkylsulfonylmethed anion, or halogenoalkylsulfonate anion, and each halogenoalkyl group is each independently substituted with 3 to 6 halogen atoms C1-C10 alkyl group.

(2) The colored resin composition for color filters in said (1) whose polymerization initiator is a photoinitiator or a thermal polymerization initiator.

(3) In the above (1) or (2), X ^- in formula (1) is bistrifluoromethanesulfonylimide anion, tristrifluoromethanesulfonyl met anion or trifluoromethylsulfonate Colored resin composition for color filters which is anion.

(4) In any one of said (1)-(3), in Formula (1), R <_2> and R <_15> -R <_18> is a C1-C4 alkyl group each independently, and R <_1> and R <_3> -R <_14> is The colored resin composition for color filters which are all hydrogen atoms.

(5) The colored resin composition for color filters in any one of said (1)-(4) which further contains either or both of a metal phthalocyanine pigment or the color material compound of following formula (2):

In the above formula, each of R _1a to R _6a independently represents a hydrogen atom, a halogen atom, an alkyl group of C 1 -C 12, an alkoxy group of C 1 -C 12, a nitro group, a carboxy group, or an alkoxycarbonyl group. Y _{1 to} Y ₄ each independently represent a hydrogen atom, a C1-C12 alkyl group, or an aryl group. X _{1 to} X ₅ each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom, a nitro group, a phenoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group, and a sulfamoyl group. Anion moiety X ⁻ represents a halogenoalkylsulfonylimide anion, a halogenoalkylsulfonylmethed anion, or a halogenoalkylsulfonate anion, wherein each halogenoalkyl group is independently 3 to 6 halogen atoms; Substituted C1-C10 alkyl group.

(6) The coloring resin composition as described in said (5) containing a metal phthalocyanine pigment.

(7) The coloring resin composition for color filters containing said metal phthalocyanine pigment and the coloring material compound of Formula (2) in said (5).

(8) In any one of (5) to (7), in formula (2), all of R _1a to R _6a are hydrogen atoms, all of Y _{1 to} Y ₄ are C ₁ -C ₄ alkyl groups, and X _The colored resin composition for color filters whose ₁ is a carboxy group, X <_2> -X <_5> is a hydrogen atom, and X <^-> is tritrifluoromethanesulfonylmethed anion.

(9) Said (1)-(4) containing the colored resin composition in any one of said (1)-(4), or the metal phthalocyanine pigment or any one or both of the color material compounds of following formula (2). The color filter which has a hardened | cured material layer of the colored resin composition for color filters in any one of 4):

In the above formula, each of R _1a to R _6a independently represents a hydrogen atom, a halogen atom, an alkyl group of C 1 -C 12, an alkoxy group of C 1 -C 12, a nitro group, a carboxy group, or an alkoxycarbonyl group. Y _{1 to} Y ₄ each independently represent a hydrogen atom, a C1-C12 alkyl group, or an aryl group. X _{1 to} X ₅ each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom, a nitro group, a phenoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group, and a sulfamoyl group. Anion moiety X ⁻ represents a halogenoalkylsulfonylimide anion, a halogenoalkylsulfonylmethed anion, or a halogenoalkylsulfonate anion, wherein each halogenoalkyl group is independently 3 to 6 halogen atoms; Substituted C1-C10 alkyl group.

(10) In the above (9), in the formula (1), R ₂ and R ₁₅ to R ₁₈ are each independently a C1-C4 alkyl group, and R ₁ and R ₃ to R ₁₄ are all hydrogen atoms, and X ⁻ Is tristrifluoromethanesulfonylmethed anion, in formula (2), all of R _1a to R _6a are hydrogen atoms, all of Y _{1 to} Y ₄ are C ₁ -C ₄ alkyl groups, and X ₁ is a carboxy group And X _{2 to} X ₅ are hydrogen atoms, and X ⁻ is tristrifluoromethanesulfonylmethed anion.

(11) A display device equipped with the color filter according to the above (9) or (10).

(12) A solid-state imaging device equipped with the color filter according to (9) or (10).

The colored resin composition for color filters of the present invention (also referred to as the colored resin composition of the present invention or the resin composition of the present invention) has a vivid color characteristic and can provide a color filter pixel excellent in heat resistance and the like. Moreover, the coloring resin composition for color filters is excellent in storage stability, even if it contains a metal phthalocyanine pigment.

The colored resin composition of this invention contains a binder resin, a solvent, a polymerization initiator (for example, a photoinitiator or a thermal polymerization initiator), a hardening | curing agent, and a specific color material compound, and if necessary, color material compounds, such as another pigment or dye, Various additives, such as surfactant, a thermosetting agent, a polymerization inhibitor, and a ultraviolet absorber, can be contained. It is not limited to these, It can use without a restriction | limiting especially as components other than a specific color material compound.

As a pixel manufacturing method using the colored resin composition of this invention, the photolithographic method and the inkjet method are mainly mentioned, The former can use the photosensitive resin composition excellent in developability using a photoinitiator, The latter necessarily requires a photoinitiator. The thermosetting resin composition can be used.

Said specific color material compound used for this invention is represented by said Formula (1).

In R <_2> and R <_15> -R <_18> of said Formula (1), as an alkyl group of C1-C30, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, 1-methylpropyl group (s-butyl, for example) Group), isobutyl group, pentyl group, 1-ethylpropyl group, 1-methylbutyl group, cyclopentyl group, hexyl group, 1-methyl pentyl group, 1-ethylbutyl group, cyclohexyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, 2-heptyl group, heptyl group, octyl group, nonyl group, decyl group , Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, aralkyl group, eicosyl group, Henicosyl group, docosyl group, tricosyl group , Tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, isoheptyl , Isooctyl group, isononyl group, isodecyl group, isododecyl group, isotridecyl group, isotetradecyl group, isopentadecyl group, isohexadecyl group, isoheptadecyl group, isooctadecyl group, isononadecyl group , Isoaralkyl group, isoicosyl group, isoencosyl group, isodocosyl group, isotricosyl group, isotetracosyl group, isopentacosyl group, isohexacosyl group, isopentacosyl group, isooctacosyl group, isononaco Real group, isotriacyl group, 1-methylhexyl group, 1-ethylheptyl group, 1-methylheptyl group, 1-cyclohexylethyl group, 1-heptyl octyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group , 4-methylcyclohexyl group, 2,6-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,3-dimethylcyclo Hexyl group, 3,3,5-trimethyl cyclohexyl group, 4-t-butylcyclohexyl group, 2-ethylhexyl group, 1- However, group, 2-adamantyl group and the like may be mentioned, as the case may be in, and is preferably C1-C6 alkyl group, and these are preferable C1-C4 alkyl group.

In R <_2> and R <_15> -R <_18> of Formula (1), a phenyl group or benzyl group may have a substituent, As this substituent, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, an isobutyl group, for example. (C1-C5) alkyl groups such as t-butyl group and pentyl group; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Sulfonic acid group; (C1-C6) alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group and hexyloxy group; Hydroxy (C1-C5) alkyl groups such as hydroxyethyl group and hydroxypropyl group; (C1-C5) alkoxy (C1-C5) alkyl groups such as methoxyethyl group, ethoxyethyl group, ethoxypropyl group and butoxyethyl group; Hydroxy (C1-C5) alkoxy groups such as 2-hydroxyethoxy group; Alkoxy (C1-C5) alkoxy groups, such as a 2-methoxyethoxy group and 2-ethoxyethoxy group; Substituted ethyl groups, such as a 2-sulfoethyl group, a carboxyethyl group, and a cyanoethyl group, are mentioned.

As R <_2> and R <_15> -R <_18> of Formula (1), each independently, a C1-C6 alkyl group is preferable and, as the case may be, a C1-C4 alkyl group is more preferable.

In R <_1> and R <_3> -R <_14> of Formula (1), as a C1-C12 alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, Hexyl group, cyclohexyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, etc. are mentioned. .

As R <_1> and R <_3> -R <_14> of Formula (1), each independently, a hydrogen atom, a chlorine atom, or an unsubstituted C1-C12 alkyl group is preferable, More preferably, it is a case of all hydrogen atoms.

As a halogen atom in Formula (1), a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.

Anion part X <^-> in said formula (1) represents halogenoalkylsulfonyl imide anion, halogenoalkylsulfonyl met anion, or halogenoalkylsulfonate anion, and each halogenoalkyl group is independent And C 1 -C 10 alkyl group substituted with 3 to 6 halogen atoms. As a halogen atom in the group, a fluorine atom is preferable.

Preferable examples of X ⁻ include bistrifluoromethanesulfonylimide anion, tristrifluoromethanesulfonylmethed anion or trifluoromethylsulfonate anion. Among them, tristrifluoromethanesulfonylmethed anion is more preferable.

As one of the preferable compounds of said Formula (1), in Formula (1), R <_2> and R <_15> -R <_18> is a C1-C4 alkyl group each independently, and R <_1> and R <_3> -R <_14> are all hydrogen atoms. And X ^- is bistrifluoromethanesulfonylimide anion, tristrifluoromethanesulfonylmethed anion or trifluoromethylsulfonate anion, and more preferably X ^- is tris Trifluoromethanesulfonylmethedanion.

Although the specific example of the color material compound of Formula (1) is shown in Table 1, this invention is not limited to these.

In the table, substituent R represents each of R ₁ to R ₁₈ in the corresponding numbers, Me represents a methyl group, Et represents an ethyl group, i-Bu represents an isobutyl group, Ph represents a phenyl group, and CH represents a cyclohexyl group. In X ^- In the case of an α has shown the methanesulfonate nilme suited anion, in the case of β, the methane sulfonyl-bis-trifluoromethyl imide anion, methyl sulfonate anion in the case of γ is trifluoroacetic tris trifluoroacetate each .

In the color material compound of the said Formula (2) which can be used together with the compound of Formula (1) in this invention, R <_1a> -R <_6a> is respectively independently a hydrogen atom, a halogen atom, a C1-C12 alkyl group, C1-C12 It is preferable that the alkoxy group, the nitro group, the carboxy group, and the alkoxycarbonyl group of the above are represented and all of R _1a to R _6a are hydrogen atoms. Y _{1 to} Y ₄ each independently represent a hydrogen atom, an alkyl group of C1-C12, or an aryl group, and either one or both of Y ₁ and Y ₂ , or Y ₃ and Y ₄ are each an alkyl group of C1-C12 (preferably C1 -C 4 alkyl group) is preferred. X _{1 to} X ₅ each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom, a nitro group, a phenoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group or a sulfamoyl group, Each of X _{1 to} X ₅ may be the same or different. Anion moiety X ⁻ represents a halogenoalkylsulfonylimide anion, a halogenoalkylsulfonylmethed anion, or a halogenoalkylsulfonate anion, wherein each halogenoalkyl group is independently 3 to 6 halogen atoms; Substituted C1-C10 alkyl group.

As a halogen atom of Formula (2), the thing similar to what was described in said Formula (1) is mentioned.

As a C1-C12 alkyl group or C1-C10 alkyl group of Formula (2), for example, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, t-butyl group, iso -Butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, a cyclohexyl group, etc. are mentioned. These alkyl groups may have a substituent, for example, a hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group , Butoxyethyl group, trifluoromethyl group, pentafluoroethyl group, carbamoyl group, carboxyl group and the like.

As a C1-C12 alkoxy group of Formula (2), the group made by attaching an oxygen atom to the alkyl group illustrated by said C1-C12 alkyl group and making it into the alkoxy group is mentioned. Also in the case of an alkoxycarbonyl group, the group which added the oxycarbonyl group (-OCO- group) to the alkyl group illustrated by said C1-C12 alkyl group, and made the alkoxycarbonyl group is mentioned.

As an aryl group of Formula (2), For example, aromatic hydrocarbon residues, such as a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a pyrenyl group, a benzopyrenyl group; Aromatic heterocycle residues such as pyridyl, pyrazyl, pyrimidyl, quinolyl, isoquinolyl, pyrrolyl, indorenyl, imidazolyl, carbazolyl, thienyl and furyl Can be. These aryl groups may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a sulfo group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, and a cyano group.

The anion part X <^-> which the color material compound of Formula (1) and Formula (2) contained in the colored resin composition of this invention has halogenoalkylsulfonyl imide anion, halogenoalkylsulfonyl met anion, or halogeno Alkylsulfonate anions are represented, and each halogenoalkyl group is each independently a C1-C10 alkyl group substituted with 3 to 6 halogen atoms. As a halogen in this halogenoalkyl group, a fluorine atom is preferable. Specific examples of X- include bistrifluoromethanesulfonylimide anion, tristrifluoromethanesulfonyl met anion, trifluoromethylsulfonate anion, and nonafluorobutylsulfonate anion. Especially tristrifluoromethanesulfonylmethed anion is preferable.

As a preferable color material compound of Formula (2), all of R <_1a> -R <_6a> are hydrogen atoms, and either or both of Y <_1> and Y <_2> or Y <_3> and Y <_4> is a C1-C12 alkyl group (preferably C1-C4). Alkyl group), and any of X _{1 to} X ₅ is a carboxy group, an alkoxycarbonyl group (preferably C1-C4 alkoxycarbonyl group) or a carboxamide group (preferably benzylaminocarbonyl group or C1 which may have hydroxy substitution) -C4 lower alkylaminocarbonyl group), and others are hydrogen atoms, and X ^- is tristrifluoromethanesulfonylmethed anion.

As a more preferable color material compound of Formula (2), all of R <_1a> -R <_6a> are hydrogen atoms, all of Y <_1> -Y <_4> are C1-C4 alkyl groups (preferably ethyl group), X <_1> is a carboxy group, X <_2> - The compound whose X <_5> is a hydrogen atom and X <^-> is tristrifluoromethanesulfonylmethed anion is mentioned.

Although the specific example of the color material compound of Formula (2) is shown in following Table 2 and Table 3, this invention is not limited to these.

As a coloring material compound used for the colored resin composition of this invention, GIHODO SHUPPAN CO., Ltd., for example. Although it is obtained by the known synthesis method as described in `` Theoretical Manufacturing Dye Chemistry '' published by Hosoda Yutaka of the publication (p. 373 to 375), a commercial product in which the anion moiety X ⁻ is chlorine anion is added, and a corresponding salt or acid is added to add a salt. It is also possible to synthesize | combine by exchanging.

When synthesize | combining the color material compound in this invention by salt exchange, the color material compound whose anion part X <^-> is chlorine anion is reacted with a reaction solvent (for example, water or methanol, ethanol, isopropanol, acetone). And water-soluble polar solvents such as N, N-dimethylformamide (hereinafter abbreviated as DMF) and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and these solvents are singly or mixed. And 0.5 to 3 equivalents of the corresponding salt or acid, are stirred at a predetermined temperature (for example, 0 to 100 ° C), and the precipitated crystals are filtered easily. Obtained.

Total solid content of the colored resin composition of this invention (It refers to the total amount of solid content which consists of a color material compound, a binder resin, a hardening | curing agent, etc. except a solvent. It is used by the same meaning after that.) The said formula contained in 100 parts of said formula (1 Content of the color material compound of () is preferably 0.1 to 60 parts by mass, preferably 1 to 30 parts, more preferably 3 to 30 parts by mass. Moreover, in some cases, the coloring material compound of Formula (1) is 1-10 mass% in the total solid of the colored resin composition of this invention, Preferably it is 2-10 mass%, More preferably, it is about 3-10 mass%, Furthermore, the colored resin composition of this invention containing about 3-8 mass% is also preferable.

When there is too much content of the color material compound of said Formula (1), a problem of precipitation and aggregation arises, or the fall of adhesiveness with a board | substrate arises because of inadequate hardening. When content is too small, there exists a tendency for sufficient color purity not to be obtained as a color characteristic.

When the solubility of the color material compound of the said Formula (1) to the colored resin composition is low, it can disperse | distribute using a dispersing agent, a dispersal auxiliary agent, etc. similarly to the pigment which is an optional component mentioned later. The color material compound of the said Formula (1) may mix 2 or more types, may be used independently, and may also mix another dye and a pigment. Moreover, since this invention relates to a blue pixel, the form used together with a well-known blue dye or violet dye, or a blue pigment or a violet pigment is also preferable, Especially the said metal phthalocyanine pigment (preferably copper phthalocyanine content) Or / and the colored resin composition of this invention which used the coloring material compound of said Formula (2) together is one of the preferable forms. Content of said metal phthalocyanine pigment (preferably copper phthalocyanine content) or the color material compound of said Formula (2) is about 0-30 mass% in the total solid of the coloring resin composition of this invention, respectively. As a sum with the color material compound of said Formula (1), it is about 2-60 mass% normally, More preferably, it is about 10-30 mass%.

When using a metal phthalocyanine pigment (preferably copper phthalocyanine), the content is about 5-30 mass% normally in the total solid of the coloring resin composition of this invention, Preferably it is 7-20 mass%. Moreover, when using together the color material compound of Formula (2), the content is about 0.5-10 mass% normally in the total solid of the coloring resin composition of this invention, Preferably it is 1-7 mass%.

As binder resin which can be used by this invention, resin which has the following property is preferable.

In other words,

(i) functioning as a dispersing agent or dispersing aid for dispersion stability during dispersion of the pigment or water-insoluble dye,

(ii) when used in the photolithography method, being soluble in an alkaline developer that can be used in the development treatment step at the time of manufacturing the color filter;

(iii) Furthermore, in order to form a good fine pattern, a polymerization initiator (for example, a photoinitiator or a thermal polymerization initiator) and a curing agent (for example, a polymerizable monomer, more specifically in light) contained in the colored resin composition of this invention are included. Synthetic monomer, or a thermopolymerizable monomer).

The colored resin composition of this invention obtained by mix | blending this binder resin has the polymerization initiator (for example, photoinitiator or thermopolymerization initiator) contained in it, the polymerizable monomer (photopolymerizable monomer or / and thermopolymerizable monomer), a formula ( Compatibility with constituent materials such as colorant compound and pigment dispersion in 1) should be good and stable so as not to cause precipitation or aggregation during storage or use.

In the case where the colored resin composition of the present invention is used in the inkjet method, alkali solubility is not particularly necessary, so that a resin having good compatibility with other color material compounds or additives can be selected.

Known resin can be used as binder resin. Preferably, a homopolymer of an ethylenically unsaturated monomer having one or more carboxyl groups / or hydroxyl groups (hereinafter also referred to as a carboxyl group-containing unsaturated monomer or a hydroxyl-containing unsaturated monomer) or an aromatic copolymerizable with the ethylenically unsaturated monomer thereof. As a copolymer with another ethylenically unsaturated monomer etc. (henceforth another unsaturated monomer) which have a hydrocarbon group or an aliphatic hydrocarbon group, a copolymer is preferable normally.

Moreover, the thing which has an epoxy group etc. to these side chains or terminal of these polymers, the epoxy acrylate resin which added the acrylate further, etc. can also be used.

Said monomer used for manufacture of binder resin, etc. may be used individually or in combination of 2 or more types, and binder resin may be sufficient as it.

As said carboxyl group-containing unsaturated monomer used by this invention,

(i) unsaturated monocarboxylic acids such as, for example, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid;

(ii) unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid;

(iii) trivalent or higher unsaturated polyvalent carboxylic acids (anhydrides),

(iv) 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl2-hydroxypropyl phthalate, 2-acryloyloxyethyl2-hydroxyethyl phthalic acid, etc. are mentioned. Can be.

The ethylenically unsaturated monomer which has these carboxy groups can be used individually or in mixture of 2 or more types. Among these, (meth) acrylic acid is more preferable.

As said hydroxyl-containing unsaturated monomer used by this invention, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, 3-hydroxypentyl (meth) Acrylate, 6-hydroxyhexyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 5-hydroxy-3-methyl-pentyl (meth) acrylic C1-C8 glycol (mono) (meth) acrylates, such as a rate and cyclohexane-1,4- dimethanol-mono (meth) acrylate; C3-C6 triol (mono or di) (meth) acrylates, such as glycerin monomethacrylate; 2- (2-hydroxyethyloxy) ethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) monomethacrylate, etc. Hydroxyl terminal polyalkylene glycol mono (meth) acrylate (preferably polyC1-C4 alkylene glycol mono (meth) acrylate); And hydroxyl group-containing (meth) acrylates. The ethylenically unsaturated monomer which has these hydroxyl groups can be used individually or in mixture of 2 or more types. As an ethylenically unsaturated monomer which has this hydroxyl group, said hydroxyl group containing (meth) acrylate is preferable normally, and hydroxy C1-C6 (meth) acrylate is more preferable.

The hydroxyl group-containing unsaturated monomer (preferably hydroxyl group-containing (meth) acrylate) can be used as a monomer for copolymerization with the aforementioned carboxyl group-containing unsaturated monomer (preferably (meth) acrylic acid).

Moreover, as said other unsaturated monomer, for example, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, o- chlor styrene, m- chlor styrene, p- chlor styrene, p- Aromatic vinyl compounds such as methoxy styrene; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) Unsaturated carboxylic acid esters (preferably a phenyl group, such as an acrylate, o-phenylphenol glycidyl ether (meth) acrylate, o-phenylphenol (meth) acrylate hydroxyethylate, and phenoxyethyl (meth) acrylate) Containing C1-C4 alkyl (meth) acrylate); Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenyl nobornyl (meth) acrylate , Cyanobornyl (meth) acrylate, isobonyl (meth) acrylate, carbonyl (meth) acrylate, menthyl (meth) acrylate, pentyl (meth) acrylate, adamantyl (meth) acrylate, dimethyla Danmanyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] deca-8-yl = (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] deca-4-methyl = (meth) acrylic Alicyclic skeleton-containing compounds (preferably C5-C10 aliphatic rings, such as latex, cyclodecyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, and t-butylcyclohexyl (meth) acrylate) (Meth) acrylate, more preferably C5- C10 aliphatic ring (meth) acrylate);

Methoxy polyethylene glycol monomethacrylate, lauryloxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, nonylphenoxypolyethylene glycol monoacrylate, nonylphenoxypolypropylene glycol Alkyl-terminated polyalkylene glycol mono (meth) acrylates, such as monoacrylate and allyloxy polyethyleneglycol- polypropylene glycol mono (meth) acrylate (preferably C1-C10 alkyl-terminated polyC2-C4 alkylene glycol (meth) ) Acrylate); Unsaturated carboxylic amino such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate Alkyl esters (preferably aminoC1-C4 alkyl (meth) acrylates); Glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylic Unsaturated carboxylic acid glycidyl esters such as late glycidyl ether (preferably epoxy group-containing (meth) acrylate, epoxy-containing C1-C6 aliphatic (meth) acrylate); Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, and methacryl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Acrylamide, methacrylamide, α-chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N- (2-hydroxyethyl) acrylamide, Unsaturated amides or unsaturated imides such as N- (2-hydroxyethyl) methacrylamide and maleimide; Aliphatic conjugated diene compounds such as 1,3-butadiene, isoprene and chloroprene; Having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polyn-butyl acrylate, polyn-butyl methacrylate, polysilicon Macromonomer etc. are mentioned. These other unsaturated monomers can be used individually or in mixture of 2 or more types.

Among these, as other unsaturated monomers, preferred are phenyl group-containing C1-C4 alkyl (meth) acrylates, C5-C10 aliphatic ring-containing (meth) acrylates, and C1-C10 alkyl-terminated polyC2-C4 alkylene glycol (meth) acrylates. (Meth) acrylates, such as a rate, an amino C1-C4 alkyl (meth) acrylate, and an epoxy group containing (meth) acrylate. More preferably, it is C1-C4 alkyl (meth) acrylate substituted by a phenyl group, C5-C10 aliphatic ring containing (meth) acrylate, etc., More preferably, it is C1-C4 alkyl (meth) acrylate substituted by a phenyl group. Most preferably benzylacrylate.

Moreover, the polymer which introduced the unsaturated double bond further in the side chain of a copolymer is also useful. For example, an acrylate or glycidyl having an alcoholic hydroxyl group such as hydroxyethyl acrylate in the maleic anhydride portion of a copolymer of styrene, vinylphenol, acrylic acid, acrylic acid ester, acrylamide or the like copolymerizable with maleic anhydride. Acrylic acid to the hydroxyl group of the copolymer of the compound which half-esterified by reacting acrylate which has epoxy groups, such as methacrylate, and the acrylate which has alcoholic hydroxyl groups, such as acrylic acid, acrylic acid ester, and hydroxyethyl acrylate The compound which made this react, etc. are mentioned. Moreover, urethane resin, polyamide, polyimide resin, polyester resin, commercially available ACA-200M (Daicel Corporation), ORGA-3060 (OSAKA ORGANIC CHEMICLA INDUSTRY LTD.), AX3-BNX02 (NIPPON SHOKUBAI CO., LTD.), UXE-3024 (NIPPON KAYAKU Co., Ltd.), UXE-3000 (NIPPON KAYAKU Co., Ltd.), ZGA-287H (NIPPON KAYAKU Co., Ltd.), TCR-1338H (NIPPON KAYAKU Co., Ltd. ), ZXR-1722H (NIPPON KAYAKU Co., Ltd.), ZFR-1401H (NIPPON KAYAKU Co., Ltd.), ZCR-1642 (NIPPON KAYAKU Co., Ltd.) can also be used.

As binder resin contained in the colored resin composition of this invention, (meth) acrylic acid copolymer resin which is a copolymer of (meth) acrylic acid (preferably methacrylic acid) and the monomer copolymerizable with it is preferable, More preferably, ( Also referred to as copolymers ((meth) acrylic acid- (meth) acrylate copolymers of metha) acrylic acid (preferably methacrylic acid) and (meth) acrylate compounds (including hydroxyl-containing (meth) acrylates). )to be. As the copolymer as the binder resin, a copolymer having an acid value of 10 to 300 (mgKOH / g) or a hydroxyl value of 10 to 200 (mgKOH / g) is preferable. More preferably, the acid value is 50-250, More preferably, it is a copolymer of about 100-200.

The molecular weight is good as long as it can play a role as a binder resin, the weight average molecular weight (Mw) (polystyrene equivalent) is usually about 2000-400000, about 3000-100000 is preferable, about 5000-70000 is more preferable, 8000- About 40000 is more preferable.

The ratio of both monomers in the (meth) acrylic acid- (meth) acrylate copolymer is not particularly limited, but considering the developability and the like, in terms of mass ratio, (meth) acrylic acid: a monomer capable of polypolymerization (preferably (Meth) acrylate) is 1: 0.5-1: 10, Preferably it is about 1: 1-1: 5.

Moreover, as said (meth) acrylate compound, said hydroxyl-containing (meth) acrylate and (meth) acrylates other than that mentioned above are mentioned. As a (meth) acrylate compound, C5-C10 aliphatic ring containing (meth) acrylate or C1-C4 alkyl (meth) acrylate which may be substituted by the said phenyl group is more preferable, and benzyl (meth) acrylate is more preferable. .

More preferred (meth) acrylic acid- (meth) acrylate copolymers are copolymers of (meth) acrylic acid with C1-C4 alkyl (meth) acrylate (preferably benzyl (meth) acrylate) which may be substituted with a phenyl group. Or a copolymer of (meth) acrylic acid and C5-C10 aliphatic ring-containing (meth) acrylate, and may be a copolymer composed only of both of them, or in a range without problems (for example, 0 to 20 mol%, preferably May contain another copolymerization component in the range of 0-10 mol%, More preferably, 0-5 mol%).

In addition, in this invention, expression of "(meth) acrylic acid" is used by the meaning of acrylic acid or methacrylic acid, or both. For example, (meth) acrylate is used in the sense of acrylate or / and methacrylate.

Generally, a dispersant and a dispersing aid are used to disperse the pigment. Therefore, when the resin composition of this invention contains a pigment, the resin composition of this invention preferably contains a dispersing agent or a dispersing agent and a dispersal auxiliary agent.

Examples of the dispersant include a dye dispersant having a good adsorption property to the pigment, a resin dispersant, a surfactant, and the like, and in the present invention, it is preferable to use them in combination. For example, as a technique of disperse | distributing a pigment using a pigment-type dispersing agent, the method of mixing the sulfonate of a pigment or its metal salt as described in said patent document 4, or its metal salt, and a substituted aminomethyl derivative are mixed with a pigment. The method of making is known as a well-known technique. As the resin-based dispersant, there are nonpolar nonionic ones, but polymer resins having an acid value, an amine value, and the like which give good pigment adsorption are common, and acrylic resins, polyurethane resins, polycarboxylic acids, polyamide resins, polyester resins, etc. Can be. As the specific example, ED211 (Kusumoto Chemicals, Ltd.), AJISPER ^RTM PB821 (Ajinomoto Fine-Techno Co., Inc.), Solsperse ^RTM 71000 (Avecia), etc. are mentioned, for example.

The content of this dispersing agent in the resin composition of this invention is about 0-30 mass% with respect to a total solid, Preferably it is about 0-20 mass%.

The binder resin (copolymer) which can be used by this invention can also synthesize | combine using a commercial item.

When manufacturing this binder resin, a polymerization initiator is used. As a specific example of the polymerization initiator used when synthesize | combining a copolymer here, (alpha), (alpha) '-azobis (isobutyronitrile), 2,2'- azobis (2-methylbutyronitrile), t -Butyl peroctoate, dit-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, etc. are mentioned. The use ratio of a polymerization initiator is 0.01-25 mass parts with respect to a total of 100 mass parts of all the monomers used for the synthesis | combination of a copolymer. Moreover, when synthesize | combining a copolymer, it is preferable to use the organic solvent demonstrated below. It is preferable that the organic solvent has sufficient dissolving power with respect to the monofunctional monomer, polymerization initiator, etc. to be used. It is preferable that the reaction temperature at the time of synthesize | combining a copolymer is 50-120 degreeC, Especially preferably, it is 80-100 degreeC. Moreover, it is preferable that reaction time is 1 to 60 hours, More preferably, it is 3 to 20 hours.

As the copolymer as the binder resin, a copolymer having an acid value of 10 to 300 (mgKOH / g) or a hydroxyl value of 10 to 200 (mgKOH / g) is preferable.

When acid value or hydroxyl value is 10 or less, developability falls.

2000-400000 are preferable and, as for the weight average molecular weight (Mw) of this copolymer, 3000-100000 are more preferable. When this weight average molecular weight is 2000 or less, or 400000 or more, a sensitivity, developability, etc. fall.

In this invention, the said binder resin can be used individually or in mixture of 2 or more types.

Content of binder resin in this invention is 0.5-99 mass parts normally with respect to 100 mass parts of total solids of a colored resin composition, Preferably it is 5-50 mass parts. In this case, when content of binder resin is less than 0.5 mass part, alkali developability may fall, or problems, such as scumming and a residual film, in the area | regions other than the part in which a pixel is formed may arise.

As a hardening | curing agent used by this invention, a light or thermal polymerization monomer in the case of radical polymerization, an epoxy resin in the case of ion hardening, a melamine hardening | curing agent, etc. are mentioned. Specific examples of these are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylic Elate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, bisphenol-A type epoxy di (meth) acrylate, bisphenol-F epoxy di (meth) Acrylate, bisphenol-fluorene type epoxydi (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane Tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylic And acrylate compounds such as 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene.

As a commercial item, KAYARAD ^RTM RP-1040 (NIPPON KAYAKU Co., Ltd.), KAYARAD ^RTM DPCA-30 (NIPPON KAYAKU Co., Ltd.), UA-33H (SHIN-NAKAMURA CHEMICAL CO., LTD.), UA-53H The (meth) acrylate compound sold by brand names, such as (SHIN-NAKAMURA CHEMICAL CO., LTD.) And M-8060 (TOAGOSEI CO., LTD.), Is mentioned.

Moreover, as a thiol type polymerization monomer, products, such as TEMPIC, TMMP, PEMP, and DPMP (made by SAKAI CHEMICAL INDUSTRY CO., LTD.), Are mentioned.

Examples of epoxy resins include NC-6000, NC-3000, EOCN-1020, XD-1000, EPPN-501H, BREN-S, NC-7300L, CELLOXITE 2021P, EHPE3150, from NIPPON KAYAKU Co., Ltd. Cyclomer M100, EPOLEADPB3600, Japan Epoxy Resin Co., Ltd. Epikote ^RTM 828, Epikote ^RTM YX8000, Epikote ^RTM YX4000, Sila-ace ^RTM S510 (CHISSO CORPORATION), TEPIC (NISSAN CHEMICAL INDUSTRIES, LTD.), Etc. are mentioned.

Moreover, as a melamine hardening | curing agent, goods, such as methylolated melamine and Mw-30 (Sanwa Chemical co., LTD.), Are mentioned. These can be used individually or in mixture of 2 or more types.

As a polymerizable monomer preferable as a hardening | curing agent, a polyfunctional (meth) acrylate compound is preferable and a 3-6 functional (meth) acrylate compound is more preferable. Pentaerythritol tri or tetra (meth) acrylate or dipentaerythritol tri-hexa meth) acrylate is mentioned as this 3-6 functional (meth) acrylate compound.

These content may be 1-80 mass parts, Preferably it is 10-60 mass parts, More preferably, it is 20-60 mass parts and also 5-30 mass parts in 100 mass parts of total solids of a colored resin composition. have.

It is preferable that the pigment | dye which can be used together with the coloring resin composition of this invention has a spectral characteristic suitable for a color filter, can be selected suitably from dye, an organic pigment, and an inorganic pigment, and can be used individually or in combination of 2 or more types as needed. It may be. These content is 0-60 mass parts in the total solid content of 100 mass parts of a colored resin composition, Preferably it is 0-30 mass parts, Moreover, Preferably it is 5-30 mass parts. These various pigments and dyes are specifically described below.

The organic pigment which can be used in combination with the present invention is not particularly limited as long as it has spectral characteristics suitable for color filters. For example, anthraquinone series, phthalocyanine series, triphenylmethane series, benzoimidazolone series and quinacridone series , Azochelate, azo, isoindolin, isoindolinone, pyrantrone, indanthrone, anthrapyrimidine, dibromoanthrone, flavantron, perylene, perinone, quinone Pigments such as nophthalone-based, thioindigo-based, dioxazine-based, quinacridone-based, and xanthene-based; Lake pigment, dye Lake pigment, etc. which insolubilized acid dye, alkaline dye, direct dye, etc. with each precipitant are mentioned. More specifically, for example, Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79; Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49, 50; Pigment violet 3, 4, 27, 39, etc. are mentioned. In particular, the metal phthalocyanine pigment which shows blue, such as Pigment Blue 15: 6 and Pigment Violet 23, is more preferable because it is good in color, tolerance, etc.

There is no restriction | limiting in particular as an inorganic pigment which can be used together in this invention, For example, a composite metal oxide pigment, carbon black, black low-dimensional titanium oxide, titanium oxide, barium sulfate, zincation, lead sulfate, a yellow lead, a bengal, a navy blue, Royal Blue, Chromium Oxide, Antimony White, Iron Black, Podium (Light Coal), Zinc Emulsified, Cadmium Yellow, Cadmium Red, Zinc, Manganese Violet, Cobalt Violet, Barium Sulfate, Metal Oxides such as Magnesium Carbonate, Metal Sulfide, Sulfate, Metal Hydroxides, metal carbonates and the like.

The dye that can be used in combination with the present invention is not particularly limited, and examples thereof include acid dyes, alkaline dyes, direct dyes, sulfide dyes, vat dyes, naphthol dyes, reactive dyes and disperse dyes. Especially, what is soluble in an organic solvent is good, but it can be used suitably by making it a dispersion also as an insoluble dye in an organic solvent.

In the above, the dye insoluble in the organic solvent can be modified by a well-known modification method. For example, in the case of an acid dye or an alkaline dye, an organic amine compound (e.g., n-propylamine, ethylhexylpropionate amine, etc.) is reacted to be modified into an amine salt dye, or the same organic amine as the sulfonic acid group. It is known to react a compound and modify it with the dye etc. which have a sulfonamide group. Amine modified by those amines can also be used in the colored resin composition of the present invention. As the specific dye, for example, solvent blue 2, 3, 4, 5, 6, 23, 35, 36, 37, 38, 43, 48, 58, 59, 67, 70, 78, 98, 102 , 104; Basic blue 7; Acidblue 80, 83, 90; Solvent violet 8, 9 as violet dye; Violet 4, 5, 14; Basic violet 10 etc. are mentioned.

As a photoinitiator added to the coloring resin of this invention used for the photography method, it is preferable to have sufficient sensitivity to the ultraviolet-ray irradiated from the ultrahigh pressure mercury lamp which can be generally used as an exposure light source, and it is a radically polymerizable optical radical initiator and an ion curable resin. And a photoacid generator or a photobase generator used in the above. In photopolymerization, it can use combining the component of the polymerization promoter called a sensitizer, such as hardening at less exposure energy. Although the photoinitiator which can be used does not have a restriction | limiting in particular, As a specific example, benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3'- dimethyl- 4-methoxy benzophenone, benzoyl benzoic acid, benzoyl Esters of benzoic acid, 4-benzoyl-4'-methyldiphenylsulfide, benzyldimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, Isopropyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, diisopropyl thioxanthone, dimethylaminomethylbenzoate, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane- 1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, methylbenzoylformate, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethyl Mino-1- (4-morpholinophenyl) -butanone-1,2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-s-triazine, 2,4-bis (tribromomethyl) -6- (4'-methoxyphenyl) -1,3 , 5-s-triazine, 2,4,6-tris (tribromomethyl) -1,3,5-s-triazine, 2,4-bis (trichloromethyl) -6- (1,3 -Benzodioxoran-5-yl) -1,3,5-s-triazine, benzophenone, benzoyl benzoic acid, 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime- O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanylphenyl) butan-1-one oxime-O- Acetate, 4,4'-bis (diethylamino) benzophenone, P-dimethylaminobenzoic acid isoamyl ester, P-dimethylaminobenzoic acid ethyl ester, 2,2'-bis (O-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, diazonaphthoquinone-based initiator, commercially available KAYACURE ^RTM DMBI, KAYACURE ^RTM BDMK, KAYACURE ^RTM BP-1 00, KAYACURE ^RTM BMBI, KAYACURE DETX-S, KAYACURE EPA ^RTM (all, NIPPON KAYAKU Co., Ltd.), ^RTM DAROCUR 1173, DAROCUR1116 (both Merck Japana), ^RTM IRGACURE 907, IRGACURE 369 ^RTM, IRGACURERTM379EG, ^RTM IRGACURE OXE -01, IRGACURE ^RT MOXE-02, IRGACURE ^RTM PAG103 (above IRGACURE is Chiba Specialty Chemicals Co., Ltd.), TME-triazine (Sanwa Chemical co., LTD.), Biimidazole (KUROGANE KASEI Co., Ltd.), STR -110, STR-1 (all are the RESPE-CHEMICAL Co., Ltd. product) etc. are mentioned.

In the case of the thermosetting resin composition used by the inkjet method etc., although a thermal polymerization initiator can be used generally, a photoinitiator can be used together as needed. Examples of the thermal polymerization initiator include azo compounds and organic peroxide compounds, but for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2 And 2'-azobis (2-methylbutyronitrile), di-t-butyl peroxide, dibenzoyl peroxide, cumylperoxy neodecanoate and the like.

These polymerization initiators can be used individually or in combination of 2 or more types as needed. These content is 0.5-50 mass parts, Preferably it is 1-25 mass parts, More preferably, it is 1-10 mass parts when the total solid of colored resin composition is 100 mass parts.

The organic solvent used in the present invention has a sufficient dissolving power to a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and the like, which are constituents of the colored resin composition, and also has a sufficient dissolving power to the monofunctional monomer, polymerization initiator, and the like used in the synthesis of the binder resin. You can use what you have. Moreover, when preparing a pigment dispersion, what can maintain dispersion stability can be used.

There is no restriction | limiting in particular if the organic solvent used for this invention can be used, As a specific example, Benzene, such as benzene, toluene, xylene; Cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; Cellosolve acetic acid esters such as methyl cellosolve acetate, ethyl cellosolve acetate, and butyl cellosolve acetate; Propylene glycol monoalkyl ether acetic acid esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; Propionic acid esters such as methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate and ethyl ethoxypropionate; Lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; Diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Acetic acid esters such as methyl acetate, ethyl acetate and butyl acetate; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone; Alcohol, such as methanol, ethanol, butanol, isopropyl alcohol, benzyl alcohol, etc. are mentioned.

As a preferable solvent, a combination of a ketone solvent and an acetate ester is usually used, More preferably, a combination of a ketone solvent and a propylene glycol monoalkyl ether acetate ester is mentioned.

These can be used individually or in combination of 2 or more types. Moreover, 40-10000 mass parts is preferable with respect to 100 mass parts of total solids of a colored resin composition, and, as for the usage-amount of an organic solvent, 100-1000 mass parts is more preferable.

It is as follows when an example of the preferable composition ratio of the colored resin composition of this invention is shown. In addition, content ratio is the mass ratio (%) contained in the total amount (total solid content) of solid content of the colored resin composition of this invention except a solvent.

The content ratio of the solid content is 3 to 30% of the color material compound of the formula (1), 5 to 50% of the binder resin, 1 to 80% of the curing agent, 0 to 60% of the dyes other than the color material compound of the formula (1) and 1 to 1 polymerization initiator. 25%. More preferably, 2 to 10% of the color material compound of the formula (1), 10 to 50% of the binder resin, 20 to 50% of the curing agent, 0 to 60% of the pigments other than the color material compound of the formula (1) and the polymerization initiator 1 to 10 %to be.

The solvent content in a preferable colored resin composition is about 100-1000 mass% (about 1-10 mass times) with respect to the total amount of solid content.

Moreover, the viscosity of the colored resin composition of this invention is about 8-20 mP * s, More preferably, it is about 10-15 mP * s at the viscosity of 25 degreeC from the convenience of application | coating etc.

The colored resin composition of this invention is manufactured by mixing and stirring said binder resin, a hardening | curing agent, a photoinitiator, a specific color material compound, an organic solvent, etc. with a resolver, a homomixer, etc. Moreover, you may add another pigment and dye as needed. When it is a pigment and dye which is low in solubility, it is preferable to mix | blend a suitable dispersing agent previously, to make a pigment or its dye dispersion with dispersers, such as a paint shaker, and to add and mix with a coloring resin composition.

As needed, the colored resin composition of this invention can add various additives, for example, a filler, surfactant, a thermal polymerization inhibitor, adhesion promoter, antioxidant, a ultraviolet absorber, an aggregation inhibitor, etc. further. Moreover, in order to remove a foreign material etc. after the preparation, the colored resin composition of this invention can also be filtered fine with a filter.

The manufacturing method of the color filter which has this hardened | cured material layer is demonstrated.

First, the colored resin composition of the present invention is coated on a substrate such as a glass substrate or a silicon substrate by a spin coating method, a roll coating method, a slit and spin coating method, a die coating method, a bar coating method, or the like, and has a film thickness of 0.1. It apply | coats so that it may become -20 micrometers, Preferably it is 0.5-5 micrometers. Subsequently, drying is carried out in a decompression chamber or the like as necessary. For example, drying is carried out under reduced pressure at a temperature of 23 to 150 ° C. for 1 to 60 minutes, more preferably at a temperature of 60 to 120 ° C. for 1 to 10 minutes. In addition, prebaking is performed on a hot plate or a clean oven to form a film. Next, a predetermined mask pattern is passed through a general photolithography method to irradiate radiation (e.g., electron beams, ultraviolet rays, preferably ultraviolet rays), and an aqueous surfactant solution, an aqueous alkali solution, or a mixed aqueous solution of a surfactant and an alkali agent Develop with As the developing method, there are a dipping method, a spray method, a shower method, a paddle method, an ultrasonic development method and the like, but any of these may be combined. The unilluminated part is removed by image development, and after rinsing with water, a postbaking process is performed. The post-baking treatment is carried out, for example, at a temperature of 130 to 300 ° C. for 1 to 120 minutes, more preferably at a temperature of 150 to 250 ° C. for 1 to 30 minutes, and a pixel formed from the colored cured film of the present invention. Get

In the above, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc. can be used as surfactant. As the alkali agent, alkali carbonates such as sodium carbonate or potassium carbonate, alkali hydroxides such as sodium hydroxide or potassium hydroxide, diethanolamine, tetramethylammonium hydrooxide and the like are used. In this invention, use of the aqueous solution containing both an alkali chemicals and surfactant is preferable. The development is usually carried out at a treatment temperature of 10 to 50 DEG C, preferably 20 to 40 DEG C, and usually at a processing time of 30 to 600 seconds, preferably 30 to 120 seconds.

The color filter which has the hardened | cured material layer of the colored resin composition of this invention is useful as a color filter suitable for the solid-state image sensor etc. which are used for a liquid crystal display device, an organic electroluminescent display, a digital camera, etc. This color filter has the patterned blue pixel which consists of hardened | cured material of the colored resin composition of this invention prepared as mentioned above.

Among the display devices of the present invention, the liquid crystal display device is fabricated in such a way that a backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter of the present invention, a polarizing film, and the like are stacked in this order. In addition, the organic EL display is produced by forming the color filter of the present invention either on or below the multilayer organic light emitting element. In addition, the solid-state image sensor is produced by, for example, providing a color filter layer of the present invention on a silicon wafer on which a transfer electrode and a photodiode are formed, and then laminating microlenses.

Example

Although an Example demonstrates this invention further in detail below, this invention is not limited to these Examples. On the other hand, in an Example, "%" means "mass%", unless it is specified. do.

Synthetic example  One

Reaction:

4,4'-bis (diethyl amino) benzophenone (5.0 g, 0.02 mol), 1-methyl-2-phenyl-1H-indole (3.2 g, 0.02 mol), phosphorus oxychloride (4.7 g, 0.03 mol) The mixture solution dissolved in toluene (10 ml) was heated and stirred at 100 ° C. for 10 hours. After cooling to room temperature, water was added and liquid-separated, the organic layer was concentrated under reduced pressure, and the compound 100 (7.5 g, 95%) was obtained.

Synthetic example  2

A solution obtained by dissolving 1.7 g of cesium salt of tristrifluoromethanesulfonium methoxide was added to 1 ml of DMF while stirring a mixed solution of compound 100 (1.0 g, 0.003 mol) in 10 ml of water and 50 ml of methanol. After stirring at room temperature for 3 hours, the precipitated crystals were filtered, washed with water and dried to obtain crystalline Compound 1 (triarylmethane compound of the present invention) (1.04 g, 54%).

Synthetic example  3

1 g of rhodamine B (TOKYO CHEMICAL INDUSTRY CO., LTD.) Of the following formula (101) and 20 g of water were thrown into a 100 ml beaker, and it stirred at room temperature for 30 minutes. The solution which melt | dissolved the cesium salt 1g of tristrifluoromethanesulfonium methoxide (TFSM) in 1 ml of DMF was dripped at this, and it stirred for 3 hours. The precipitated dye was filtered, washed with water and dried to obtain 0.7 g of TFSM salt (Compound 2-3) of rhodamine B. Maximum absorption wavelength: 560 nm (cyclohexanone)

Synthetic example  4 (synthesis of binder resin (copolymer))

Into a 500 ml four-necked flask, 160 g of methyl ethyl ketone, 10 g of methacrylic acid, 33 g of benzyl methacrylate, 1 g of α, α'-azobis (isobutyronitrile) were added, and nitrogen gas was introduced into the flask for 30 minutes while stirring. Flowed in. Then, it heated up to 80 degreeC and stirred as it is at 80-85 degreeC for 4 hours. After completion of the reaction, the mixture was cooled to room temperature to obtain a colorless, transparent and uniform copolymer solution. This was precipitated in a 1: 1 mixed solution of isopropyl alcohol and water, filtered, the solids were taken out and dried to obtain a copolymer (A) of methacrylic acid and benzyl methacrylate.

The polystyrene reduced weight average molecular weight of the obtained copolymer (A) was 18000, and the acid value was 152.

Example  One

5.4 g of copolymer (A) as a binder resin, 6 g of KAYARAD ^RTM DPHA (trade name, dipentaerythritol hexaacrylate, NIPPON KAYAKU Co., Ltd.) as a photopolymerizable monomer, IRGACURE ^RTM 907 (Ciba specialty chemicals) as a photopolymerization initiator Co., Ltd.) 1.5g and 0.6 g of KAYACURE ^RTM DETX-S (NIPPON KAYAKU Co., Ltd.), 0.6 g of compound 1 of Synthesis Example 2, 20 g of cyclohexanone as a solvent and propylene glycol monomethyl ether acetate (PGMEA) 8.6 g , Each was mixed and the colored resin composition of this invention was obtained.

Example  2

CI pigment blue 15: 6 (copper phthalocyanine pigment) / AJISPER ^RTM PB821 / Solsperse ^RTM 5000 / PGMEA (solvent) = 15.0 / 6.0 / 1.0 / 78.0 (mass ratio) after mixing at 400, 0.3 g zirconia bead 400 g Then, the process was performed for 60 minutes with the paint shaker, the zirconia bead was removed by filtration, and the pigment dispersion 1 was obtained. 19g of pigment dispersions 1 were added to the coloring resin composition of this invention obtained in Example 1, and the coloring resin composition of this invention containing the copper phthalocyanine pigment was obtained.

Example  3

To the colored resin composition obtained in Example 2, 0.6 g of a compound 2-3 (TFSM salt of Rhodamine B) obtained in Synthesis Example 3 was further added, which contained a copper phthalocyanine pigment and the colorant compound of formula (2). The colored resin composition of this invention was obtained.

Comparative Example  One

The colored resin composition of Comparative Example 1 was obtained in the same manner as in Example 1 except that Compound 1 in Example 1 was changed to Basic Blue 7 which is a conventional bright blue dye.

The colored resin composition (Examples 1-3 and Comparative Example 1) obtained above was apply | coated on a separate glass substrate, respectively. The exposed part was hardened by prebaking the obtained apply | coated board | substrate on 80 degreeC x 100 second conditions, and then exposing through the mask which has a pattern. Subsequently, it developed with the aqueous alkali solution containing surfactant, rinsed with water, and it heated at 200 degreeC, and obtained the color filter which has a pixel pattern. The color filter obtained had 5 micrometers x 5 micrometers (horizontal x vertical) resolution in line and space, and residue, peeling of a pixel, etc. were not confirmed.

Evaluation of heat resistance

The board | substrate for evaluation of heat resistance was created by full surface exposure, without using the exposure mask which has a pattern as follows.

That is, as described in the said Example 1, the resin composition of each Example and the resin composition of the comparative example were apply | coated to a separate glass substrate, respectively, and photocuring of the apply | coated resin composition was performed by front exposure. Subsequently, the process was performed for 5 minutes at 200 degreeC of post-baking, and the color filter (substrate for evaluation) which has the clear blue characteristic all was created.

The evaluation test was done using the obtained evaluation board | substrate as follows.

Each evaluation board | substrate obtained above was processed at 200 degreeC for 120 minutes, and the spectral transmittance of the evaluation board | substrate before and behind a process was measured with the spectrophotometer "Shimazu Corporation UV-3150." Color difference (ΔEab) before and after heat treatment was calculated and evaluated from the chromaticity in the XYZ color system calculated from the measured spectral transmittance.

Table 4 shows the evaluation results of the heat resistance.

From the evaluation results in Table 4, the color filters obtained in Examples 1 to 3 of the present invention are significantly smaller in color difference before and after heat treatment than the color filters of Comparative Example 1 obtained using conventional dyes. The result was shown.

That is, it turns out that the outstanding color filter which improved heat resistance is obtained from the resin composition of this invention containing the color material compound of Formula (1).

Moreover, the color filter using the colored resin composition of Example 2 containing both the color material compound of Formula (1) and a copper phthalocyanine pigment is the color using the colored resin composition of Example 1 only for the color material compound of Formula (1). The color filter using the coloring resin composition of Example 3 which has more excellent heat resistance than the filter and further contains the color material compound of Formula (1), copper phthalocyanine, and the color material compound of Formula (2) has more excellent heat resistance. Able to know.

Moreover, although the colored resin composition of Example 2 and 3 contains the copper phthalocyanine pigment, insoluble content etc. did not precipitate but the storage stability of the resin composition was also favorable.

As mentioned above, the colored resin composition of this invention containing the color material compound of dye-type Formula (1) has wide applicability, and is useful as a colored resin composition for next-generation color filters.

(Industrial availability)

As mentioned above, the coloring resin composition of this invention containing the color material compound of dye-type Formula (1) has the characteristic suitable for the next generation color filter, and obtains the high quality and highly reliable color filter pixel from this resin composition. Can be. Moreover, since it can mix and use with a pigment satisfactorily according to a use, the resin composition has wide applicability and its industrial applicability is large.

Claims (12)

Colored resin composition for color filters containing the color material compound of the following formula (1), binder resin, a solvent, a polymerization initiator, and a hardening | curing agent:

In this formula,
R ₂ and R ₁₅ to R ₁₈ each independently represent a hydrogen atom, a C1-C30 alkyl group, a phenyl group or a benzyl group,
R ₁ and R ₃ to R ₁₄ each independently represent a hydrogen atom, a halogen atom and an alkyl group of C 1 -C 12,
X ⁻ represents halogenoalkylsulfonylimide anion, halogenoalkylsulfonylmethed anion, or halogenoalkylsulfonate anion,
Each halogenoalkyl group is each independently a C1-C10 alkyl group substituted with 3 to 6 halogen atoms. The colored resin composition for color filters of Claim 1 whose polymerization initiator is a photoinitiator or a thermal polymerization initiator. The coloring for color filters according to claim 1, wherein X ^- in formula (1) is bistrifluoromethanesulfonylimide anion, tristrifluoromethanesulfonyl met anion or trifluoromethylsulfonate anion. Resin composition. The colored resin composition for color filters according to claim 1, wherein in Formula (1), R ₂ and R ₁₅ to R ₁₈ are each independently a C1-C4 alkyl group, and R ₁ and R ₁₃ to R ₁₄ are all hydrogen atoms. . The colored resin composition for color filters according to any one of claims 1 to 4, further comprising any one or both of a metal phthalocyanine pigment or a colorant compound of the following formula (2):

In this formula,
R _1a to R _6a each independently represent a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, a carboxyl group, and an alkoxycarbonyl group,
Y _{1 to} Y ₄ each independently represent a hydrogen atom, a C1-C12 alkyl group, or an aryl group. X _{1 to} X ₅ each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a halogen atom, a nitro group, a phenoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group, and a sulfamoyl group,
Anion moiety X ⁻ represents a halogenoalkylsulfonylimide anion, a halogenoalkylsulfonylmethed anion, or a halogenoalkylsulfonate anion, wherein each halogenoalkyl group is independently 3 to 6 halogen atoms; Substituted C1-C10 alkyl group. The colored resin composition of Claim 5 containing a metal phthalocyanine pigment. The colored resin composition for color filters of Claim 5 containing a metal phthalocyanine pigment and the color material compound of Formula (2). A compound according to claim 5, wherein in formula (2), all of R _1a to R _6a are hydrogen atoms, all of Y _{1 to} Y ₄ are C ₁ -C ₄ alkyl groups, X ₁ is a carboxy group, and X _{2 to} X ₅ are a hydrogen atom, X ^- is tris trifluoromethane sulfonate nilme suited anionic color filter colored resin composition. The colored resin composition according to any one of claims 1 to 4, or any one of claims 1 to 4 further comprising either or both of a metal phthalocyanine pigment or a colorant compound of the following formula (2). The color filter which has a hardened | cured material layer of the colored resin composition for color filters of any one of Claims:

In this formula,
R _1a to R _6a each independently represent a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a nitro group, a carboxyl group, and an alkoxycarbonyl group,
Y _{1 to} Y ₄ each independently represent a hydrogen atom, an alkyl group of C1-C12, an aryl group, X _{1 to} X ₅ each independently represent a hydrogen atom, an alkyl group of C1-C12, an alkoxy group of C1-C12, a halogen atom, Nitro group, phenoxy group, carboxy group, alkoxycarbonyl group, sulfo group or sulfamoyl group,
Anion moiety X ⁻ represents a halogenoalkylsulfonylimide anion, a halogenoalkylsulfonylmethed anion, or a halogenoalkylsulfonate anion, wherein each halogenoalkyl group is independently 3 to 6 halogen atoms; Substituted C1-C10 alkyl group. The compound according to claim 9, wherein in formula (1), R ₂ and R ₁₅ to R ₁₈ are each independently a C1-C4 alkyl group, R ₁ and R ₃ to R ₁₄ are all hydrogen atoms, and X ⁻ is a tristri; Fluoromethanesulfonylmethed anion, in formula (2), all of R _1a to R _6a are hydrogen atoms, all of Y _{1 to} Y ₄ are C1-C4 alkyl groups, X ₁ is a carboxy group, X ₂ X <_5> is a hydrogen atom, and X <^-> is tristrifluoromethanesulfonylmethed anion. A display device equipped with the color filter according to claim 9. The solid-state image sensor which mounted the color filter of Claim 9.