JP2008304766A - Colored resin composition for color filter, color filter, organic el display and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter which satisfies heat resistance required in a color display production process and excels in the color purity and transmittance of blue pixels, and to provide an organic EL display and a liquid crystal display device which satisfy both of high color reproducibility and high luminance by using such color filters. <P>SOLUTION: A colored resin composition for color filters is provided which comprises (a) a binder resin and (b) a solvent and is prepared by dissolving a triarylmethane dye of a specific structure represented by general formula (I). The color filter obtained using the composition, the organic EL display and the liquid crystal display device are also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored resin composition capable of providing a blue pixel of a color filter having excellent spectral characteristics, a color filter having a pixel formed using the same, an organic EL display formed using the color filter, and The present invention relates to a liquid crystal display device.

In recent years, color liquid crystal display devices and organic EL displays have attracted attention as flat displays, and color filters are used for these displays.
For example, a color liquid crystal display device includes, as an example, a black matrix, a colored layer composed of a plurality of colors (usually three primary colors of red (R), green (G), and blue (B)), a transparent electrode, and an alignment layer. The color filter substrate provided, the thin film transistor (TFT element), the counter electrode substrate provided with the pixel electrode and the alignment layer, the two substrates are opposed to each other with a predetermined gap, sealed with a sealing member, and liquid crystal is placed in the gap. There is a transmissive liquid crystal display device which is roughly configured from a liquid crystal layer formed by injecting a material. There is also a reflective liquid crystal display device in which a reflective layer is provided between the color filter substrate and the colored layer.

  In principle, an organic EL display has an organic EL element having a structure in which an organic EL light emitting layer is sandwiched between an anode and a cathode. However, in practice, color display is possible using the organic EL element. In order to obtain an organic EL display, (1) a method of arranging organic EL elements that emit light of each of the three primary colors, (2) a method of combining an organic EL element that emits white light with a color filter layer of the three primary colors, and ( 3) There is a CCM method that combines an organic EL element that emits blue light and a color conversion layer (CCM layer) that performs color conversion from blue to green and blue to red, respectively.

Needless to say, the method of (1) is characterized by high color reproducibility due to the use of organic EL elements of each color. As described in Patent Documents 3 to 4, by placing a color filter corresponding to each color organic EL element, an improvement in color reproducibility and an improvement in contrast by absorbing reflected light can be expected. Therefore, it is considered as one of the promising methods.
In addition, in the white organic EL + color filter system (2) and the CCM system (3), it is only necessary to use one type of organic EL element that emits light of the same color. In addition, it is not necessary to align the characteristics of the organic EL elements of each color, and the number of processes and materials can be reduced in terms of manufacturing cost.

  In an organic EL device using a color filter and a color conversion method comprising a color conversion filter and an organic illuminant, heat resistance required in the color display manufacturing process, weather resistance when used as a display, and For those that require high-definition images, it is the mainstream to use color filters created by the pigment dispersion method. Red, blue or green pigments in the photosensitive resin solution have a particle size of 1 μm or less. After the finely dispersed material is applied onto a glass substrate, pixels are formed in a desired pattern by photolithography (Japanese Patent Publication No. 4-37987, Japanese Patent Publication No. 4-39041, etc.).

  For color filters, improvements in color purity, saturation, and light transmission are required. Conventionally, for the purpose of improving the light transmission, the content of the color pigment relative to the photosensitive resin in the image forming material is reduced. A method has been adopted in which the thickness of the pixel formed by the image forming material is reduced or the pixel formed is made thinner. However, in these methods, the saturation of the color filter itself is lowered, the entire display becomes whitish, and the vividness of the color necessary for display is sacrificed. If it raises, the whole display will become dark, and in order to ensure brightness, the light quantity of a backlight must be enlarged, and there exists a problem of causing the increase in the power consumption of a display.

On the other hand, for the purpose of improving the amount of light transmission, there is known a method of finely dispersing the particle size of pigment particles to ½ or less of the coloration wavelength (Kei Hashizume, Color Material Association magazine, In December 1967, p608), blue pigments have a shorter coloration wavelength than other red and green pigments. In this case, further fine dispersion is required, which increases costs and stabilizes dispersion. Become.
On the other hand, color filters using dyes as colorants are still being developed. For example, Patent Document 1 describes a color filter provided with a blue filter layer containing a triallylamine dye represented by the following general formula.

  Patent Document 2 describes a color filter using a polymer containing a polymerizable triphenylmethane dye represented by the following formula.

(At least one of R ^{1 in} the above formula is a specific polymerizable group containing a carbon-carbon double bond)
However, the color filters using the dyes described in these documents have a problem that the spectral characteristics are insufficient.
Japanese Patent Laid-Open No. 2002-14222 JP 2000-162429 A Japanese Patent Laid-Open No. 10-3990 JP 2007-12370 A

  An object of the present invention is to provide a colored resin composition that can provide a blue pixel of a color filter having excellent spectral characteristics and that also satisfies the heat resistance required in the color display manufacturing process described above. . It is another object of the present invention to provide a color filter excellent in color purity and transmittance of a blue pixel, an organic EL display having good blue purity, and a liquid crystal display device by using such a colored resin composition.

The present inventors have found that the above problem can be solved by using a triallylamine dye having a specific structure as a blue pixel forming material of a color filter, and have reached the present invention.
That is, the gist of the present invention is as follows.
(1) A colored resin composition for a color filter, comprising (a) a binder resin, and (b) a solvent, and dissolving a triarylmethane dye represented by the following general formula (I).

(In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represents an alkyl group, R ⁵ represents an alkyl group or an aryl group which may have a substituent, and X ⁻ represents Cl ⁻ Or ArSO ₃ ⁻
Indicates. Ar represents an aromatic ring, and the aromatic ring may be substituted with an amino group which may have a substituent. )
(2) The colored resin composition for a color filter according to (1), further comprising (d) a pigment.
(3) The colored resin composition for a color filter according to (1) or (2), further comprising (c) a monomer.
(4) The colored resin composition for a color filter according to any one of (1) to (3), further comprising (e) a photopolymerization initiation system and / or a thermal polymerization initiation system.
(5) The colored resin composition for a color filter according to any one of (1) to (4), wherein the compound represented by the general formula (I) is dissolved in an amount of 1 to 50% by weight in the total solid content. object.
(6) A color filter having pixels formed using the colored resin composition for a color filter according to any one of (1) to (5).
(7) An organic EL display or a liquid crystal display device formed using the color filter according to (6).

  According to the present invention, the heat resistance required in the color display manufacturing process is also satisfied, and a color filter excellent in color purity and transmittance of a blue pixel can be obtained, and by using such a color filter, The light emission of the organic EL display and the light emission of the backlight of the color filter can be efficiently taken out, and an organic EL display and a liquid crystal display device that achieve both high color reproducibility and high luminance can be provided.

Embodiments of the present invention will be described in detail below, but these are examples of embodiments, and the present invention is not limited to these contents.
The present invention resides in a colored resin composition for a color filter, which contains (a) a binder resin and (b) a solvent and dissolves the triarylmethane dye represented by the general formula (I). .

  In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ". Further, “total solid content” means all components of the colored resin composition of the present invention other than the solvent components described later.

[Compound represented by formula (I)]
The triarylmethane dye used in the present invention is represented by the following general formula (I) as described above.

(In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represents an alkyl group, R ⁵ represents an alkyl group or an aryl group which may have a substituent, and X ⁻ represents Cl ⁻ Or ArSO ₃ ⁻
Indicates. Ar represents an aromatic ring, and the aromatic ring may be substituted with an amino group which may have a substituent. )
R ¹ , R ² , R ³ and R ⁴ each independently represents an alkyl group. The alkyl group is preferably an alkyl group generally found in triarylmethane dyes, and is usually an alkyl group having about 1 to 4 carbon atoms. Of these, a methyl group and an ethyl group are more preferable. R ¹ , R ² , R ³
And R ⁴ may be the same or different, but are preferably the same from the viewpoint of dye production.

R ⁵ represents an alkyl group or an aryl group which may have a substituent. R ⁵ is preferably a substituent generally found in triarylmethane dyes, and usually includes an alkyl group having about 1 to 4 carbon atoms and a phenyl group optionally substituted with the alkyl group. An ethyl group, a phenyl group or a p-tolyl group is more preferable, and an ethyl group is particularly preferable.
X ^- is Cl ^- or ArSO ₃ ^- shows the. From the viewpoint of high heat resistance of the compound, X ⁻
rSO ₃ ^- it is preferred. Ar represents an aromatic ring, and the aromatic ring may be substituted with an amino group which may have a substituent. The aromatic ring may be either an aromatic ring consisting of carbon alone or an aromatic ring containing a hetero atom, and may have a condensed ring structure, and is usually a 5- or 6-membered monocyclic ring or 2 It is a condensed ring. Among them, an aromatic ring composed of only carbon is preferable, and a benzene ring or a naphthalene ring is more preferable. When Ar is a naphthalene ring, the substitution position may be the 1-position or the 2-position.

The aromatic ring may be substituted with an amino group which may have a substituent. Examples of the substituent of the amino group include an alkyl group having about 1 to 4 carbon atoms, an aryl group which is a 5- or 6-membered monocyclic or bicondensed ring, and the like.
Specific examples of the compound represented by the general formula (I) are given below, but the present invention is not limited thereto.

General formula (I) a triarylmethane dye represented by the X ^- is Cl ^- if a can either be purchased commercially or can be synthesized by known methods. As a synthesis method,
The method described in “Review Synthetic Dyes” (Horiguchi Hiroshi, Sankyo Publishing, 1968) is helpful.
A dye having X ⁻ represented by ArSO ₃ ⁻ can be purchased commercially, but can be synthesized, for example, by adding a corresponding sulfonic acid sodium salt to a dye having X ⁻ represented by Cl ⁻ and performing salt exchange. . Specifically, it can be synthesized by dissolving a dye represented by X ⁻ in Cl ⁻ in a reaction solvent, adding the corresponding sodium sulfonate, stirring, and then removing the precipitate by filtration. The amount of sodium sulfonate added is, for example, about 1 to 3 equivalents. Examples of the reaction solvent include water; alcohol solvents such as methanol, ethanol and 2-propanol; or a mixed solvent thereof. Examples of the reaction temperature include 0 to 40 degrees.

  In the colored resin composition of the present invention, the compound represented by the general formula (I) is usually dissolved in an amount of 1 to 50% by weight, preferably 2 to 30% by weight, based on the total solid content. If the amount of the compound is too large, problems such as poor solubility in solvents, precipitation due to poor compatibility with (a) binder resin described later, and deterioration in heat resistance of the resulting pixel may occur. If the amount is too small, the objectives of achieving both high color reproducibility and high luminance may not be sufficiently achieved.

[Colored resin composition]
The colored resin composition of the present invention can be used without particular limitation as long as it can be used as a color filter forming material. For example, any type of resin composition such as a thermosetting resin composition described in JP-A-60-184202 and a photopolymerizable resin composition described later may be used. The resin, (b) solvent, and triarylmethane dye represented by the general formula (I) are essential components.

Hereinafter, the case where the colored resin composition of the present invention is a photopolymerizable resin composition will be described in detail, but the present invention is not limited thereto.
[(A) Binder resin]
As (a) the binder resin, as described above, a preferable resin is different depending on what means is used for the colored resin composition to be cured. However, in the case of a thermosetting resin composition, it is necessary to form an image by further providing a positive resist layer or the like for pattern formation. From the viewpoint of simplicity of the process, the photopolymerizable resin composition Things are preferred.

  In this case, examples of the binder resin (a) include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000. -56118, JP-A-2003-233179, and other publicly known polymer compounds described in JP-A No. 2003-233179 can be used, and the following resins (a-1) to (a-5) are preferred. Is mentioned.

(A-1): An unsaturated monobasic acid is added to at least part of the epoxy group of the copolymer with respect to the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer. Alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction or the addition reaction
(A-2): Carboxyl group-containing resin
(A-3): Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin (a-2).
(A-4): Acrylic resin
(A-5): Epoxy acrylate resin having a carboxyl group Each of these resins will be described below.

(A-1): “Unsaturated monobasic acid in at least part of the epoxy group of the copolymer relative to the copolymer of the epoxy group-containing (meth) acrylate and other radical polymerizable monomer Or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction "
As one particularly preferable resin, “the copolymer has 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radical polymerizable monomer. Resin obtained by adding unsaturated monobasic acid to 10 to 100 mol% of epoxy group, or alkali-soluble resin obtained by adding polybasic acid anhydride to 10 to 100 mol% of hydroxyl group generated by the addition reaction ".

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is preferably a mono (meth) acrylate having a structure represented by the following general formula (1).

In formula (1), R ^{1 to} R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁷ and R ⁸ each independently represent a hydrogen atom, 3 alkyl groups or may be linked to form a ring.
In the formula (1), the ring formed by connecting R ⁷ and R ⁸ is preferably an aliphatic ring, which may be saturated or unsaturated, and has 5 to 6 carbon atoms. Is preferred.

Among these, the structure represented by the general formula (1) is preferably a structure represented by the following formula (1a), (1b), or (1c).
By introducing these structures into the binder resin, when the colored resin composition of the present invention is used for a color filter or a liquid crystal display element, the heat resistance of the colored resin composition is improved, or the colored resin composition is used. It is possible to increase the intensity of the pixel formed by using.

  In addition, the mono (meth) acrylate which has a structure represented by General formula (1) may be used individually by 1 type, and may use 2 or more types together.

  As the mono (meth) acrylate having the structure represented by the general formula (1), various known ones can be used as long as the structure has the structure, and those represented by the following general formula (2) are particularly preferable. .

In the formula (2), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents the structure of the general formula (1).
In the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (1) is: Among repeating units derived from “other radical polymerizable monomers”, those containing 5 to 90 mol% are preferable, those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable. preferable.

  The “other radical polymerizable monomer” other than the mono (meth) acrylate having the structure represented by the general formula (1) is not particularly limited. Specifically, for example, vinyl aromatics such as styrene, styrene α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; butadiene, 2,3-dimethylbutadiene, isoprene, Dienes such as chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (Meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid isoamyl, (meth) acrylic acid hexyl, (meta ) -2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Cyclopentyl acid, cyclohexyl (meth) acrylate, (meth) acrylate-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid naphthyl, (meth) acrylic acid anthracenyl, (meth) acrylic acid anthraninonyl, (meth) acrylic acid piperonyl, (meth) acrylic acid salicylate, (meth) acrylic acid furyl, (Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofuryl, (meth) acrylic acid pyranyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl, (meth) acrylic acid cresyl, (meth) acrylic acid-1 , 1,1-trifluoroe Chill, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as cumyl, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic acid amides such as N-di-iso-propylamide and (meth) acrylic acid anthracenylamide; Vinyl compounds such as anilic rilates, (meth) acryloylnitriles, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate; diethyl citraconic acid, diethyl maleate, Unsaturated dicarboxylic acid diesters such as diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; N- (meta ) Acrylyl phthalimide and the like.

  Among these “other radically polymerizable monomers”, at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is used to impart excellent heat resistance and strength to the colored resin composition. It is effective to use In particular, in the repeating unit derived from “another radical polymerizable monomer”, the content of the repeating unit derived from at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is 1 to 70 mol. %, Preferably 3 to 50 mol%.

A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Specific examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate. Propylene glycol monoalkyl ether acetates; acetate esters such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol and butyl carbitol; triethylene glycol Dialkyl ethers; propylene glycol dialkyl Ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane and decane Petroleum petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more. The amount of these solvents used is usually 30 to 1000 parts by weight, preferably 50 to 800 parts by weight, with respect to 100 parts by weight of the resulting copolymer. If the amount of solvent used is outside this range, it will be difficult to control the molecular weight of the copolymer.

  The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can do. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy-2-ethyl. Hexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (T-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxide Oxydicarbonate, diisopropyl -Oxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1- Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like can be mentioned. Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide. Among these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 weight part with respect to a total of 100 weight part of the monomer used for a copolymerization reaction, Preferably it is 1-10 weight part.

  The copolymerization reaction may be carried out by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or by adding the monomer to which the radical polymerization initiator has been added. Alternatively, the reaction may be performed dropwise in a solvent that has been heated and stirred. Further, the monomer may be added dropwise while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions can be freely changed according to the target molecular weight.

  In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

If the amount of the epoxy group-containing (meth) acrylate is too small, the addition amount of the polymerizable component and the alkali-soluble component described later may be insufficient, while the amount of the epoxy group-containing (meth) acrylate is too large and other radicals are present. When there are too few polymerizable monomers, heat resistance and intensity | strength may become inadequate.
Subsequently, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali) are added to the epoxy group portion of the copolymer of the epoxy resin-containing (meth) acrylate and another radical polymerizable monomer. A soluble component).

As the unsaturated monobasic acid to be added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These 1 type may be used independently and may use 2 or more types together.

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. If the addition ratio of the unsaturated monobasic acid is too small, there is a concern about the adverse effect of the remaining epoxy group on the stability over time of the colored resin composition. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%. If the addition ratio is too large, the remaining film ratio at the time of development may decrease, and if it is too small, the solubility may be insufficient. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be.
Moreover, in order to improve developability, you may add the glycidyl ether compound which does not have a polymerizable unsaturated group to some produced | generated carboxyl groups.

Both of these may be added.
Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. As commercial products, for example, trade names “Denacol EX-111”, “Denacol EX-121”, “Denacol EX-141”, “Denacol EX-145”, “Denacol EX-146”, “Denacol EX-146” manufactured by Nagase Chemical Industries, Ltd. Denacol EX-171 "," Denacol EX-192 "and the like.

Incidentally, the structure of such a resin is described in, for example, JP-A-8-297366 and JP-A-2001-89533, and is already known.
3000-100000 are preferable and, as for the weight average molecular weight (Mw) of polystyrene conversion measured by GPC of the above-mentioned binder resin, 5000-50000 are especially preferable. If the molecular weight is less than 3000, heat resistance and film strength may be inferior. If it exceeds 100,000, the solubility in a developer tends to be insufficient. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

(A-2): Carboxyl group-containing linear alkali-soluble resin The carboxyl group-containing linear alkali-soluble resin is not particularly limited as long as it has a carboxyl group, and is usually a polymerizable monomer containing a carboxyl group. It is obtained by polymerizing a monomer.
Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Adipic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2 -(Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyl Oxybutyl succinic acid, 2- (meta Vinyl monomers such as acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; Monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone; hydroxyalkyl (meth) acrylate to succinic acid, maleic acid, phthalic acid, or Examples thereof include monomers added with acids such as anhydrides or anhydrides. A plurality of these may be used.

Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.
In addition, the carboxyl group-containing linear alkali-soluble resin may be obtained by copolymerizing the above carboxyl group-containing polymerizable monomer with another polymerizable monomer having no carboxyl group.
Other polymerizable monomers are not particularly limited, but methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate , Benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy (Meth) acrylic esters such as ethyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; vinyl aromatics such as styrene and its derivatives Vinyl compounds such as N-vinylpyrrolidone; N-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide; polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl Examples thereof include macromonomers such as (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, and polycaprolactone macromonomer. These may be used in combination.

  Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, They are butyl (meth) acrylate, isobutyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide.

  The carboxyl group-containing linear alkali-soluble resin may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and the like. Is mentioned. By copolymerizing these with the above-mentioned various monomers, a resin having a carboxyl group and a hydroxyl group can be obtained.

  Specific examples of the carboxyl group-containing linear alkali-soluble resin include (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and cyclohexyl. Polymeric monomers that do not contain hydroxyl groups such as (meth) acrylate and cyclohexylmaleimide, and hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate (Meth) acrylic acid and (meth) acrylic acid such as methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc. ester A copolymer of (meth) acrylic acid and styrene; a copolymer of (meth) acrylic acid, styrene and α-methylstyrene; a copolymer of (meth) acrylic acid and cyclohexylmaleimide, etc. Is mentioned.

From the viewpoint of excellent pigment dispersibility, a copolymer resin containing benzyl (meth) acrylate is particularly preferable.
The acid value of the carboxyl group-containing linear alkali-soluble resin in the present invention is usually 30 to 500 KOH mg / g, preferably 40 to 350 KOH mg / g, and more preferably 50 to 300 KOH mg / g.

  Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-20000 normally, Preferably it is 3000-50000, More preferably, it is 4000-30000. If the weight average molecular weight is too small, the stability of the colored resin composition tends to be inferior. If it is too large, the solubility in a developer tends to deteriorate when used in a color filter or a liquid crystal display device described later. .

(A-3): (a-2) Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group part of the resin (a-2) Epoxy group-containing unsaturated compound in the carboxyl group part of the carboxyl group-containing resin A resin to which a compound is added is also particularly preferable.
The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.

  For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- Acyclic epoxy group-containing unsaturated compounds such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but from the viewpoints of heat resistance and dispersibility of the pigment described later, alicyclic epoxy group-containing unsaturated compounds are used. preferable.

Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group and the like. or,
The ethylenically unsaturated group is preferably derived from a (meth) acryloyl group, and suitable alicyclic epoxy group-containing unsaturated compounds are represented by the following general formulas (3a) to (3m). Compounds.

In formulas (3a) to (3m), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group, R ¹³ represents a divalent hydrocarbon group, and n is an integer of 1 to 10.
In general formulas (3a) to (3m), the alkylene group represented by R ¹² preferably has 1 to 10 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group, and a methylene group, an ethylene group, and a propylene group are preferable. As the hydrocarbon group R ^13, preferably has 1 to 10 carbon atoms, alkylene group, a phenylene group, and the like.

These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
Among these, a compound represented by the general formula (3c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
In order to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the (a-2) carboxyl group-containing resin, a known method can be used. For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are converted into a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride. A quaternary ammonium salt such as pyridine, triphenylphosphine, etc. in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours. Saturated compounds can be introduced.

The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 KOH mg / g, preferably 20 to 150 KOH mg / g, more preferably 30 to 150 KOH mg / g.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-100000 normally, Preferably it is 4000-50000, More preferably, it is 5000-30000.

(A-4): Acrylic resin (a-4) The acrylic resin refers to a polymer obtained by polymerizing acrylic acid and / or acrylic acid ester as monomer components. Preferred acrylic resins include, for example, (a-4-1): a polymer obtained by polymerizing monomer components containing (meth) acrylic acid and benzyl (meth) acrylate, and (a-4-2): The polymer formed by superposing | polymerizing the monomer component which has the compound shown by following General formula (4) and / or (5) as an essential can be mentioned.

In formula (4), R ^1a and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In formula (5), R ^1b represents a hydrogen atom or an alkyl group which may have a substituent, L ³ represents a divalent linking group or a direct bond, and X is represented by the following formula (6). A group or an adamantyl group which may be substituted;

In Formula (6), R ^2b , R ^3b and R ^4b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group, L ¹ and L ² represent a divalent linking group, L ³ represents a divalent linking group or a direct bond, and two or more of L ¹ , L ² and L ³ may be bonded to each other to form a ring.
(A-4-1): a polymer formed by polymerizing monomer components including (meth) acrylic acid and benzyl (meth) acrylate
A polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate is preferably used in terms of high affinity with the pigment.

  The ratio of the (meth) acrylic acid and benzyl (meth) acrylate in the monomer component is not particularly limited, but (meth) acrylic acid in the total monomer component is usually 10 to 90% by weight, preferably 15%. -80% by weight, more preferably 20-70% by weight. Moreover, benzyl (meth) acrylate is 5 to 90 weight% normally in all the monomer components, Preferably it is 15 to 80 weight%, More preferably, it is 20 to 70 weight%. If the amount of (meth) acrylic acid is too large, the surface of the coating film tends to be rough during development, and if it is too small, development may be impossible. Further, if the amount of benzyl (meth) acrylate is too much or too little, dispersion tends to be difficult.

(A-4-2): a polymer obtained by polymerizing a monomer component essentially comprising the compound represented by formula (4) and / or (5)
First, the compound of General formula (4) is demonstrated.
In the ether dimer represented by the general formula (4), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^1a and R ^2a is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 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 or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. R ^1a and R ^2a may be the same type of substituent or different substituents.

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like. Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be used alone or in combination of two or more.

  Although the ratio of the ether dimer in the monomer component when obtaining the (a-4) acrylic resin is not particularly limited, it is usually 2 to 60% by weight, preferably 5 to 5% in all monomer components. It is 55% by weight, more preferably 5 to 50% by weight. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight product during polymerization, or may be easily gelled. On the other hand, if the amount is too small, the transparency, heat resistance, etc. There is a possibility that the performance of the coating film becomes insufficient.

Then, the compound of General formula (5) is demonstrated.
In general formula (5), R ^1b preferably represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
More preferably, they are a hydrogen atom and a methyl group.
In the general formula (6), the organic groups represented by R ^2b , R ^3b , and R ^4b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, or an acyl group. Carboxyl group or acyloxy group, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a cycloalkenyl group having 3 to 18 carbon atoms. Group, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, or an acyloxy group having 1 to 15 carbon atoms, and more preferably. Is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms.

Preferred substituents among R ^2b , R ^3b and R ^4b are a hydrogen atom, a hydroxyl group,
10 alkyl groups.
L ¹ and L ² are divalent linking groups, L ³ is not particularly limited as long as it is a divalent linking group or a direct bond, but at least either L ¹ or L ² is a linking group having 1 or more carbon atoms. Is preferred. L ¹ , L ² and L ³ are each independently a direct bond, alkylene having 1 to 15 carbon atoms, —O—
, -S-, -C (= O)-, alkenylene having 1 to 15 carbon atoms, phenylene, or a combination thereof is preferable.

As a preferable combination of L ¹ , L ² and L ³ , L ³ is a direct bond, alkylene having 1 to 5 carbon atoms, or a ring formed by bonding with R ^3b or R ^4b, and L ¹ and L ² are C1-C5 alkylene.
Moreover, as a preferable thing of General formula (6), the compound shown by following General formula (7) can be mentioned.

In the formula (7), R ^2b , R ^3b , R ^4b , L ¹ and L ² have the same meaning as in the formula (6), and R ^5b and R ^6b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, Represents an amino group or an organic group.
In the general formula (7), the organic groups represented by R ^5b and R ^6b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, or An acyloxy group and the like, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, and 1 carbon atom. -15 alkoxy group, C1-C15 alkylthio group, C1-C15 acyl group, C1-carboxyl group, or C1-C15 acyloxy group, more preferably C1-C15. Or an alkyl group having 10 to 10 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms.

Preferred substituents among R ^5b and R ^6b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
In addition, the alkyl group of R ^1b , the organic groups of R ^2b , R ^3b and R ^4b , the divalent linking group of L ¹ , L ² and L ³ , and the adamantyl group of X are each independently a substituent. Specific examples thereof may include the following substituents.

Halogen atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group A linear or branched alkyl group having 1 to 18 carbon atoms such as n-heptyl group, n-octyl group and t-octyl group; carbon number such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and adamantyl group A cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group and a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyl A linear or branched alkoxy group having 1 to 18 carbon atoms such as a xyl group, t-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, t-octyloxy group; methylthio group, Ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, amylthio group, t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, a linear or branched alkylthio group having 1 to 18 carbon atoms such as t-octylthio group; an aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; carbon such as benzyl group and phenethyl group Aralkyl group having 7 to 18 carbon atoms; straight chain or branched chain having 2 to 18 carbon atoms such as vinyloxy group, propenyloxy group, hexenyloxy group Alkenyloxy group; represented by -OCOR ^18; carboxyl group; an acyl group represented by -COR ^17; vinylthio group, propenylthio group, alkenylthio group linear or branched 2 to 18 carbon atoms such as hexenyl thio group An acyloxy group represented by —NR ¹⁹ R ²⁰ ; an acylamino group represented by —NHCOR ²¹ ; a carbamate group represented by —NHCOOR ²² ; a carbamoyl group represented by —CONR ²³ R ²⁴ ; Carboxylic acid ester group represented by ²⁵ ; sulfamoyl group represented by —SO ₃ NR ²⁶ R ²⁷ ; sulfonic acid ester group represented by —SO ₃ R ²⁸ ; 2-thienyl group, 2-pyridyl group, furyl group , Oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide A saturated or unsaturated heterocyclic group such as a side group; a trialkylsilyl group such as a trimethylsilyl group;

R ^{17 to} R ²⁸ are each a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or An aralkyl group which may have a substituent is represented.
Moreover, the positional relationship of the said substituent is not specifically limited, When it has a some substituent, it may be same or different.

  Specific examples of the compound represented by the general formula (5) include the following.

  In the monomer component constituting the (a-4-2) polymer according to the present invention, the ratio of the general formula (5) is not particularly limited, but usually 0.5 to 60% by weight in the total monomer component. The amount is preferably 1 to 55% by weight, more preferably 5 to 50% by weight. If the amount is too large, the dispersion stability of the dispersion may be lowered when used as a dispersant. On the other hand, if the amount is too small, the soil stain aptitude may be lowered.

(A-4-3) (a-4) Acrylic resin
The (a-4) acrylic resin in the present invention preferably has an acid group, including the polymers described in (a-4-1) and (a-4-2). By having an acid group, the resulting colored resin composition can be cured by a crosslinking reaction in which an acid group and an epoxy group react to form an ester bond (hereinafter abbreviated as acid-epoxy curing). Or a composition in which an uncured part can be visualized with an alkali developer. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more.

  In order to introduce an acid group into an acrylic resin, for example, a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter referred to as “monomer for introducing an acid group”) May be used as a monomer component. In addition, when using "monomer which can provide an acid group after superposition | polymerization" as a monomer component, the process for providing an acid group as mentioned later is required after superposition | polymerization.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of the monomer capable of adding an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate.

Only one type of monomer for introducing these acid groups may be used, or two or more types may be used.
When the monomer component for obtaining the acrylic resin also includes the monomer for introducing the acid group, the content ratio is not particularly limited, but usually 5 to 70% by weight in the total monomer component %, Preferably 10 to 60% by weight.

Moreover, (a-4) acrylic resin may have a radically polymerizable double bond.
In order to introduce a radical polymerizable double bond into the acrylic resin, for example, “monomer capable of imparting a radical polymerizable double bond after polymerization” (hereinafter referred to as “monomer for introducing a radical polymerizable double bond”). )) As a monomer component, and then a treatment for imparting a radical polymerizable double bond as described later may be performed.

  Examples of the monomer capable of imparting a radical polymerizable double bond after polymerization include, for example, a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride Monomers: Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

(A-4) In the case where the monomer component for obtaining the acrylic resin also includes a monomer for introducing the radical polymerizable double bond, the content ratio is not particularly limited. It is 5-70 weight% in a monomer component, Preferably it is 10-60 weight%.
When the (a-4) acrylic resin of the present invention is a polymer having the compound of the general formula (4) as an essential monomer component described in the section (a-4-2), an epoxy group It is preferable to have.

In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as “monomer for introducing an epoxy group”) may be polymerized as a monomer component.
Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one kind or two or more kinds.

(A-4) When the monomer component for obtaining the acrylic resin also includes the monomer for introducing the epoxy group, the content ratio is not particularly limited, but usually all monomer components The content is 5 to 70% by weight, preferably 10 to 60% by weight.
(A-4) The monomer component for obtaining the acrylic resin may contain other copolymerizable monomers, if necessary, in addition to the essential monomer component.

  Examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as; aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadienes such as butadiene and isoprene; Substituted butadiene compounds; ethylene, propylene, vinyl chloride , Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate and the like.

Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.
Further, in particular, when a part or all of the acrylic resin (a-4) is used as a dispersant as described later, it is preferable to use benzyl (meth) acrylate, and the content thereof is usually a total amount. It may be 1 to 70% by weight, preferably 5 to 60% by weight in the body component.

When the monomer component for obtaining the acrylic resin also contains the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by weight or less, more preferably 85% by weight or less. .
Next, (a-4) A manufacturing method (polymerization method) of the acrylic resin will be described.
There is no particular limitation on the polymerization method of the monomer component, and various conventionally known methods can be adopted, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are the types and ratios of the monomer components used. Depending on the molecular weight of the target polymer. Regarding the polymerization temperature, the polymerization temperature is preferably 40 to 150 ° C, more preferably 60 to 130 ° C. Regarding the polymerization concentration, the polymerization concentration is preferably 5 to 50%, more preferably 10 to 40%.

  Moreover, what is necessary is just to use the solvent used by normal radical polymerization reaction when using a solvent at the time of superposition | polymerization. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform; Dimethyl sulfoxide and the like Is mentioned. These solvents may be used alone or in combination of two or more.

  When the monomer component is polymerized, a polymerization initiator may be used as necessary. Although there is no restriction | limiting in particular in a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) and the like. These polymerization initiators may be used alone or in combination of two or more.

The amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is not gelled. It is usually 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomer components, in that thousands to tens of thousands of polymers can be obtained.
Moreover, you may add a chain transfer agent for molecular weight adjustment. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate, and α-methylstyrene dimer. Preferred are n-dodecyl mercaptan and mercaptoacetic acid, which can be reduced and easily available. When using a chain transfer agent, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but without gelation. It is usually 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomer components, in that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained.

In addition, when the compound of the general formula (4) is used as an essential monomer component, it is considered that the cyclization reaction of the ether dimer proceeds simultaneously in the polymerization reaction. The conversion rate is not necessarily 100 mol%.
When the acrylic resin is obtained, when the acid group is introduced by using the monomer capable of imparting the acid group described above as the monomer component, it is necessary to perform a treatment for imparting the acid group after polymerization. . The treatment varies depending on the type of monomer used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride What is necessary is just to add acid anhydrides, such as a thing. When a monomer having an epoxy group such as glycidyl (meth) acrylate is used, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or first ( An acid such as meth) acrylic acid may be added, and an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like may be added to the resulting hydroxyl group. When a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

When obtaining the acrylic resin, when the radical polymerizable double bond is introduced by using the monomer capable of imparting the radical polymerizable double bond described above as the monomer component, the radical polymerizable double bond is obtained after the polymerization. It is necessary to perform processing for granting a bond.
The treatment varies depending on the type of monomer used. For example, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( A compound having an epoxy group and a radically polymerizable double bond such as (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether may be added. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate is added. Just do it. When a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether is used, ) A compound having an acid group such as acrylic acid and a radical polymerizable double bond may be added.

  Although the weight average molecular weight of (a-4) acrylic resin of this invention is not restrict | limited in particular, Preferably the weight average molecular weight of polystyrene conversion measured by GPC is 2000-200000, More preferably, it is 4000-100000. When the weight average molecular weight exceeds 200,000, the viscosity may become too high to form a coating film, and when it is less than 2,000, sufficient heat resistance tends to be hardly exhibited.

When the acrylic resin has an acid group, a preferable acid value is 30 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g. When the acid value is less than 30 mgKOH / g, it may be difficult to apply to alkali development, and when it exceeds 500 mgKOH / g, the viscosity tends to be too high to form a coating film.
Of the acrylic resin components, the polymer having the compound represented by the general formula (4) as an essential monomer component is a compound known per se, such as JP-A 2004-300203 and Examples thereof include compounds described in Japanese Unexamined Patent Publication No. 2004-300204.

(A-5): Epoxy acrylate resin having carboxyl group Epoxy acrylate resin is an α, β-unsaturated monocarboxylic acid added to the epoxy resin or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety. And further by reacting with a polybasic acid anhydride. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc., manufactured by Yuka Shell Epoxy Co., Ltd.) Epoxy resin obtained by the reaction of alcoholic hydroxyl group and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F-type resin (for example, oily shell epoxy) "Epicoat 807", "EP-4001", "EP-4002", "EP-4004 etc.") manufactured by the company, epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin and epichlorohydrin (for example, Japan “NER-74” manufactured by Kayaku Co., Ltd. 6 ”(epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg“ YX-4000 ”manufactured by Yuka Shell Epoxy), phenol novolac type epoxy resin (eg Nippon Kayaku) “EPPN-201” manufactured by Yakuhin, “EP-152”, “EP-154” manufactured by Yuka Shell Epoxy, “DEN-438” manufactured by Dow Chemical Co.), (o, m, p-) cresol Novolac type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC” manufactured by Nissan Chemical Co., Ltd.), Phenolmethane type epoxy resin (for example, “EPPN-501”, “EPN-502”, “Nippon Kayaku Co., Ltd.” PPN-503 ”), fluorene epoxy resin (for example, cardo epoxy resin“ ESF-300 ”manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (“ Celoxide 2021P ”,“ Celoxide EHPE ”manufactured by Daicel Chemical Industries, Ltd.) ), Dicyclopentadiene type epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol (for example, “XD-1000” manufactured by Nippon Kayaku Co., Ltd., “EXA-7200” manufactured by Dainippon Ink, Japan “NC-3000” and “NC-7300” manufactured by Kayaku Co., Ltd.) and epoxy resins represented by the following structural formula (see Japanese Patent No. 2878486) can be suitably used.

These may be used alone or in combination of two or more.
Another example of the epoxy resin is a copolymerization type epoxy resin. Examples of the copolymerization type epoxy resin include glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like (hereinafter referred to as “first component of copolymerization type epoxy resin”) and one other than these. Functional ethylenically unsaturated group-containing compound (hereinafter referred to as “second component of copolymerization type epoxy resin”), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Ethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerin mono (meth) acrylate, the following general formula (8 ) One or more selected, reacting the city include a copolymer obtained by.

In Formula (8), R ⁶¹ represents hydrogen or an ethyl group, R ⁶² represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10.
Examples of the compound of the general formula (8) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate; methoxydiethylene glycol mono ( Examples thereof include alkoxy polyethylene glycol (meth) acrylates such as meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate.

As for the molecular weight of the said copolymerization type epoxy resin, about 1000-200000 is preferable. The amount of the first component of the copolymerization type epoxy resin used is preferably 10% by weight or more, particularly preferably 20% by weight or more, preferably 70% by weight based on the second component of the copolymerization type epoxy resin. % By weight or less, particularly preferably 50% by weight or less.
As such a copolymer type epoxy resin, specifically, “CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation, “CP-50S”, “CP-50M”, “CP-20MA” and the like are exemplified.

  The molecular weight of the raw material epoxy resin is usually in the range of 200 to 200,000, preferably 300 to 100,000, as the weight average molecular weight in terms of polystyrene measured by GPC. If the weight average molecular weight is less than the above range, there are many cases where a problem occurs in the film forming property. Conversely, if the resin exceeds the above range, gelation easily occurs during the addition reaction of α, β-unsaturated monocarboxylic acid. May become difficult.

Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is highly reactive. Therefore, it is preferable.
Examples of α, β-unsaturated monocarboxylic acid esters having a carboxyl group in the ester moiety include acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylate-2-succinoyloxyethyl, methacrylate-2-malenoyloxyethyl, methacrylate-2-phthaloyloxyethyl, methacrylate-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred. These may be used alone or in combination of two or more.

  The addition reaction of an α, β-unsaturated monocarboxylic acid or ester thereof with an epoxy resin can be carried out by using a known method, for example, by reacting at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. can do. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

  The amount of α, β-unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1, relative to 1 equivalent of the epoxy group of the raw material epoxy resin. Equivalent range. If the amount of α, β-unsaturated monocarboxylic acid or ester thereof used is small, the amount of unsaturated groups introduced is insufficient, and the subsequent reaction with the polybasic acid anhydride becomes insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, α, β-unsaturated monocarboxylic acid or ester thereof remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  The polybasic acid anhydride to be further added to the epoxy resin to which the α, β-unsaturated carboxylic acid or ester thereof is added includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetra Carboxylic acid dianhydride and the like, preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Biphenyltetracarboxylic dianhydride Particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be carried out by continuing the reaction under the same conditions as the addition reaction of α, β-unsaturated carboxylic acid or ester thereof.
The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mg-KOH / g, more preferably in the range of 20 to 140 mg-KOH / g. If the acid value of the resin is too small, the alkali developability is poor, and if the acid value of the resin is too large, the curing performance tends to be inferior.

  Other examples of the epoxy acrylate resin having a carboxyl group include a naphthalene-containing resin described in JP-A-6-49174; JP-A 2003-89716, JP-A 2003-165830, JP-A 2005-325331, JP-A 2001-354735. Examples of the fluorene-containing resin described in the gazette include resins described in JP-A No. 2005-126684, JP-A No. 2005-55814, JP-A No. 2004-295084, and the like.

Moreover, the commercially available epoxy acrylate resin which has a carboxyl group can also be used, and "ACA-200M" by Daicel Corporation etc. can be mentioned as a commercial item, for example.
As the binder resin, for example, an acrylic binder described in JP-A-2005-154708 can also be used.
Of the various binder resins described above, (a-1): “The copolymer is preferably a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer. A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group possessed, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .

  As (a) binder resin in this invention, 1 type may be used independently among the above-mentioned various binder resins, and 2 or more types may be used together. The above-mentioned various binder resins are used in combination with a dispersant, which is an optional component, which will be described later, in particular, with no undissolved matter remaining in the non-image area on the substrate, and excellent adhesion to the substrate, with a high concentration. The effect that a color pixel can be formed is obtained, which is preferable.

  In the colored resin composition of the present invention, the content of the (a) binder resin is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less, preferably in the total solid content. Is 60% by weight or less. When the content of the binder resin is less than this range, the film becomes fragile and the adhesion to the substrate may be lowered. On the other hand, when the amount is larger than this range, the permeability of the developing solution to the exposed portion increases, and the surface smoothness and sensitivity of the pixel may deteriorate.

[(B) Solvent]
The colored resin composition of the present invention comprises (b) a solvent as an essential component. The solvent has a function of adjusting the viscosity by dissolving or dispersing each component contained in the colored resin composition.
The solvent (b) may be any solvent as long as it can dissolve or disperse each component constituting the colored resin composition, and it is preferable to select a solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120-170 ° C.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl. Glycol monoalkyl ethers such as ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as propyl, butyl 3-methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like. These solvents may be used alone or in combination of two or more.

Among the above solvents, glycol monoalkyl ethers are preferred from the viewpoint of solubility of the triarylmethane dye of the present invention. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of the solubility of various components in the composition.
Further, for example, when a pigment (c) described later is included as an optional component, a glycol alkyl ether acetate is further provided from the viewpoint that the balance of coatability, surface tension, etc. is good and the solubility of the constituent components in the composition is relatively high. It is more preferable to use a mixture. In addition, in the composition containing the pigment (c), the glycol monoalkyl ethers have high polarity and tend to aggregate the pigment, so that the storage stability is lowered, for example, the viscosity of the colored resin composition is increased. There is a case. From this point, the ratio of (b) glycol monoalkyl ethers in the solvent is preferably 5% to 50%, more preferably 5% to 30%.

  From the viewpoint of suitability for a slit coat system compatible with recent large substrates, it is also preferable to use a solvent having a boiling point of 150 ° C. or higher. The content of such a high-boiling solvent is preferably 3% to 50%, more preferably 5% to 40%, and particularly preferably 5% to 30% with respect to the solvent (b). If the amount of the high-boiling solvent is too small, for example, coloring material components may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if too large, the drying speed of the composition will be slow, which will be described later. There is a concern that problems such as tact defects in the vacuum drying process and prebaked pin marks may be caused in the color filter manufacturing process.

The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be separately contained.
The colored resin composition of the present invention may be used for color filter production by an ink jet method. In the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several to several tens of pL, so the solvent evaporates and concentrates before landing on the periphery of the nozzle mouth or in the pixel bank. There is a tendency to dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable that the solvent (c) includes a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. Moreover, it is preferable that the high boiling point solvent whose boiling point is 180 degreeC or more is 50 weight% or more in (c) organic solvent. When the high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the ink droplets may not be sufficiently exhibited.

  In the colored resin composition of the present invention, the content of the (b) solvent is not particularly limited, but the upper limit is usually 99% by weight. When the solvent exceeds 99% by weight, the concentration of each component excluding the solvent becomes too small, which may be inappropriate for forming a coating film. On the other hand, the lower limit of the solvent content is usually 75% by weight, preferably 80% by weight, and more preferably 82% by weight in consideration of the viscosity suitable for coating.

[(C) Pigment]
The colored resin composition of the present invention may contain (c) a pigment within a range not impairing the effects of the present invention in order to improve heat resistance.
As the pigment (c), for example, when forming a pixel of a color filter, pigments of various colors such as blue and purple can be used. Examples of the chemical structure include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The following “CI” means a color index (CI).

  Examples of blue pigments include C.I. I. 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. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

  Examples of purple pigments include C.I. I. 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. Of these, C.I. I. Pigment violet 19 and 23, and more preferably C.I. I. Pigment Violet 23.

In addition, examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, and chromium oxide.
The above various pigments can be used in combination. For example, in order to adjust the chromaticity, a blue pigment and a violet pigment can be used in combination as the pigment.
These pigments are used after being subjected to a dispersion treatment so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.3 μm or less.

  In the colored resin composition of the present invention, the content ratio of the pigment (c) is usually 80% by weight or less, preferably 50% by weight or less in the total solid content, and 100 parts by weight of the triarylmethane dye of the present invention. The content is usually 2000 parts by weight or less, preferably 1000 parts by weight or less. (C) When the proportion of the pigment is too large, the effect of achieving both high color reproducibility and high brightness by the triarylmethane dye may be diminished, and sufficient image forming properties may not be obtained.

[(D) Monomer]
The colored resin composition of the present invention preferably contains (d) a monomer. (D) The monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but may be referred to as an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred.

The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system described later when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the (d) monomer in this invention means the concept opposite to what is called a polymeric substance, and also contains a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.
Examples of the ethylenic compound include unsaturated carboxylic acid such as (meth) acrylic acid, ester of monohydroxy compound and unsaturated carboxylic acid, ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid, aromatic polyhydroxy Esters obtained by esterification reaction of an ester of a compound with an unsaturated carboxylic acid, an unsaturated carboxylic acid and a polyvalent carboxylic acid and a polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound, poly Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting an isocyanate compound and a (meth) acryloyl group-containing hydroxy compound.

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. Moreover, itaconic acid ester in which the (meth) acrylic acid portion of these acrylates is replaced with itaconic acid portion, crotonic acid ester in which crotonic acid portion is replaced, or maleic acid ester in which maleic acid portion is replaced.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate and the like. The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

Other examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, pentaerythritol or (meth) acrylic acid ester of dipentaerythritol is more preferable, and dipentaerythritol hexa (meth) acrylate is particularly preferable.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used. If necessary, (d) a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination.

  A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg · KOH / g, and particularly preferably 5 to 30 mg · KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution properties tend to be lowered. If it is too high, the production and handling may be difficult, and the photopolymerization performance may be deteriorated or the surface smoothness of the pixel may be cured. May be inferior. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  In the present invention, more preferred polyfunctional monomers having an acid group are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate which are commercially available as “TO1382” manufactured by Toagosei Co., Ltd. It is a mixture containing the main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

  In the colored resin composition of the present invention, the content ratio of these (d) monomers is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content, Usually, it is 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The ratio to the colorant described later is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably Is 100% by weight or less, more preferably 80% by weight or less.

If the amount of the monomer is too small, the photocuring may be insufficient and may cause poor adhesion during development. Conversely, if the amount is too large, the photocuring is too strong and the cross-section after development becomes an inversely tapered shape. In addition, the solubility may be lowered to cause peeling and development, or may cause a defect.
[(E) Photopolymerization initiation system and / or thermal polymerization initiation system]
The curable resin composition of the present invention preferably includes (e) a photopolymerization initiation system and / or a thermal polymerization initiation system for the purpose of curing the coating film, but the curing method may be other than that using the initiator. Good.

  In particular, when the curable resin composition of the present invention contains a resin having an ethylenic C = C double bond as the component (a) or an ethylenic compound as the component (d), light is directly emitted. A photopolymerization initiating system that has a function of generating a polymerization active radical and / or a thermal polymerization initiating system that generates a polymerization active radical by heat by being absorbed or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction. It is preferable to mix | blend with a resin composition. In the present invention, the component (e) as the photopolymerization initiation system is a photopolymerization initiator (hereinafter arbitrarily referred to as (e1) component) to an accelerator (hereinafter arbitrarily referred to as (e2) component), It means a mixture in which an additive such as a sensitizing dye (hereinafter arbitrarily referred to as component (e3)) is used in combination.

[Photopolymerization initiation system]
The colored resin composition of the present invention may further contain a photopolymerization initiation system. The photopolymerization initiation system is usually used as a mixture of a photopolymerization initiator and an additive such as a sensitizing dye and a polymerization accelerator added as necessary, and directly absorbs light or is photosensitized. It is a component having a function of generating a polymerization active radical by causing a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator constituting the photopolymerization initiation system include titanocene derivatives described in JP-A-59-152396, JP-A-61-151197, etc .; Hexaarylbiimidazole derivatives described in JP-A Nos. 11-174224 and 2000-56118; halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives described in JP-A-10-39503 , Radical activators such as N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Examples thereof include oxime ester derivatives described in Japanese Utility Model Publication No. 2000-80068.

Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1 monoyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny- 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

  Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl). ) Imidazole dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4 ′ -Methoxyphenyl) -4,5-diphenylimidazole dimer and the like.

  Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Examples of halomethylated triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl). ) -S-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s -Triazine etc. are mentioned.

  Examples of the α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamylbenzoe 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- ( 4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like That.

The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime) and the like.
Other benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (pmethoxyphene Le) acridine derivatives such as acridine; 9,10-dimethyl-benz phenazine phenazine derivatives such as; anthrone derivatives such as benzanthrone etc. may be mentioned.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives and thioxanthone derivatives are more preferable.
Examples of the polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, Mercapto compounds having a heterocyclic ring such as 2-mercaptobenzimidazole; or mercapto compounds such as aliphatic polyfunctional mercapto compounds.

Each of these photopolymerization initiators and polymerization accelerators may be used alone or in combination of two or more.
In the colored curable resin composition of the present invention, the content of these photopolymerization initiation systems is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 40% by weight in the total solid content. Hereinafter, it is preferably 30% by weight or less. If this content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed part in the developer will decrease, leading to poor development, or the initiator itself. The brightness may decrease due to the influence.

  Further, a sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681 JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP 5-210240, may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p- Ethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (P-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine P-dialkylaminophenyl group-containing compounds such as Of these, 4,4'-dialkylaminobenzophenone is most preferred. A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

In the colored curable resin composition of the present invention, the content ratio of these sensitizing dyes is usually 0% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight or more in the total solid content. Moreover, it is usually 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less.
If this content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.

[Thermal polymerization initiation system]
Specific examples of the thermal polymerization initiation system (thermal polymerization initiator) used in the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used.
As the azo compounds, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexene-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2,2-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2 , 2′-azobis [N- (2-propenyl) -2-ethylpropionamide], 2,2′-azobis [N-butyl-2-methylpropionamide], 2,2′-azobis (N-cydo (Rohexyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionate), 2,2′-azobis (2 , 4,4-trimethylpentene) and the like. Among these, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and the like are preferable. .

  Examples of the organic peroxide include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like. Specifically, diisobutyryl peroxide, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3, 3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di (2-ethoxyethyl) peroxy Dicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t -Butyl peroxypivale Di (3,5,5-trimethylhexanoyl) peroxide, di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di ( 4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-butylperoxy) -2-methyl Cyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2 , 5-Di- (3-methylbenzoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-di- Methyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2, 2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl 4,4-di- (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene , Dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, p-menthane hydroperoxide, 2 , 5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl Hydroperoxide, t-butyltrimethylsilyl peroxide, 2,3-dimethyl-2,3-diphenylbuta Include a mixture of di (3-methylbenzoyl) peroxide and benzoyl (3-methylbenzoyl) peroxide and dibenzoyl peroxide.

  If the proportion of the thermal polymerization initiator is too small, the film is not sufficiently cured, and the durability as a color filter may be insufficient. If the amount is too large, the degree of thermal shrinkage increases, and cracking and cracking may occur after thermosetting. Moreover, the tendency for storage stability to fall is seen. Therefore, it is preferable to select in the range of 0 to 30% by weight, particularly 0 to 20% by weight, based on the total solid content of the curable resin composition of the present invention.

[Optional ingredients]
The colored curable resin composition of the present invention includes a surfactant, an organic carboxylic acid or / and an organic carboxylic acid anhydride, a plasticizer, and a triarylmethane represented by the general formula (I) in addition to the above components. It may contain dyes other than system pigments, thermal polymerization inhibitors, storage stabilizers, surface protective agents, adhesion improvers, development improvers and the like. Moreover, when it contains (c) a pigment as a coloring agent, you may contain a dispersing agent and a dispersing aid. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used.

[Method for Preparing Colored Resin Composition]
Next, a method for preparing the colored resin composition of the present invention will be described.
First, the triarylamine dye represented by the above general formula (I) is composed of (a) a binder resin as an essential component, and (b) a solvent, and in some cases, an optional component (d) monomer or (e) A colored resin composition is obtained by mixing with a photopolymerization initiation system, a surfactant, and other components to obtain a uniform solution. In mixing, stirring is preferably performed until the dye is sufficiently dissolved. Further, since fine dust may be mixed in each step such as mixing, it is preferable to filter the obtained ink-like liquid with a filter or the like.

In addition, when the (c) pigment is used in combination as the colorant, first, the compound represented by the general formula (I), (c) the pigment, (b) the solvent, and optional dispersing agents and dispersing aids Are weighed in predetermined amounts, and in the dispersion treatment step, (c) the pigment is dispersed to form an ink-like liquid. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing this dispersion treatment, the pigment is made into fine particles, so that the coating characteristics of the colored resin composition are improved and the transmittance of the product color filter substrate and the like is improved.

  When dispersing the pigment, it is preferable to appropriately use (a) a part of the binder resin and a dispersion aid as appropriate. Moreover, when performing a dispersion process using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the ink-like liquid and the size of the sand grinder apparatus.

  To the ink-like liquid obtained by the dispersion treatment, (a) a binder resin, which is an essential component, and (b) a solvent, and in some cases, an optional component (d) monomer or (e) a photopolymerization initiation system, A colored resin composition is obtained by mixing the surfactant and other components to obtain a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and mixing, since a fine dust may mix, it is preferable to filter the obtained ink-like liquid with a filter etc.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. This is supplied onto the substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a pixel of a color filter, a liquid crystal display device (panel) and an organic EL display using them will be described.

[Color filter pixels]
The pixel of the color filter can be formed by various methods as will be described later. Here, the case of forming by photolithographic method using a photopolymerizable colored resin composition will be described in detail, but the manufacturing method is not limited to this.
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; acrylic resins such as polymethyl methacrylate; sheets made of thermoplastic resins such as polysulfone resins; Thermosetting resin sheets such as unsaturated polyester resins; or various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. For these transparent substrates, surface treatment such as corona discharge treatment or ozone treatment, thin film formation treatment with various resins such as silane coupling agents and urethane resins, etc. Etc. may be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When a thin film forming process is performed using various resins, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less.

A color filter can be produced by providing a black matrix on the above-described transparent substrate and further forming pixel images of red, green and blue colors.
The black matrix is formed on the transparent substrate using the light shielding metal thin film or the colored resin composition of the present invention.
As the light-shielding metal material, chromium compounds such as chromium metal, chromium oxide, chromium nitride, nickel and tungsten alloy, etc. are used, and these may be laminated in a plurality of layers. These light shielding metal thin films are generally formed by a sputtering method, and a desired pattern is formed in a film shape by a positive photoresist.

  For chromium, an etchant mixed with ceric ammonium nitrate and perchloric acid and / or nitric acid is used. For other materials, etching is performed using an etchant according to the material, and finally positive. A black matrix can be formed by stripping the mold photoresist with a dedicated stripper. In this case, first, a thin film of these metals or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, a coating film of a positive photoresist resin composition is formed on the thin film. Next, the coating film is exposed and developed using a photomask having a repetitive pattern such as a stripe, a mosaic, and a triangle to form an image. Thereafter, this coating film can be etched to form a black matrix.

  Moreover, you may form a black matrix using the photopolymerizable composition containing a black (c) pigment. For example, black obtained by mixing black pigments such as carbon black, graphite, iron black, titanium black or the like, or a mixture of pigments such as red, green, and blue appropriately selected from inorganic or organic pigments Using a colored resin composition containing a pigment, a black matrix can be formed in a manner similar to the method of forming red, green, and blue pixel images described later.

  For black photopolymerizable composition, on transparent substrate, for red, green and blue colored resin compositions, on resin black matrix forming surface formed on transparent substrate, or chromium compound or other light shielding metal material A pixel image of each color is formed on the metal black matrix forming surface formed by using the above processes through coating, heat drying, image exposure, development, and thermosetting.

  On a transparent substrate provided with a black matrix, a colored resin composition containing a color material of one of red, green, and blue is applied and dried, and then a photomask is overlaid on the coating film. Then, a pixel image is formed by image exposure, development, and if necessary, heat curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue. In this invention, the colored resin composition of this invention mentioned above is used for formation of a blue pixel.

  As a method for supplying the colored resin composition to the substrate, there are conventionally known methods such as a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method and the like. Can be mentioned. Of these, the slit and spin method and the die coating method are preferable. That is, as described above, the colored resin composition of the present invention can provide a coating film having a smooth and beautiful surface without lowering the yield because aggregated foreign matter is hardly generated at the tip of the dispensing nozzle. In addition, there is no coating unevenness during the coating or drying unevenness in the subsequent drying step, and a layer having an extremely smooth surface can be formed through an exposure step, a development step, a heat treatment step, and the like.

The coating conditions by the slit-and-spin method and the die coating method may be appropriately selected depending on the composition of the colored resin composition, the type of color filter to be produced, and the like. For example, in both methods, the lip width at the nozzle tip is preferably 50 to 500 μm, and the distance between the nozzle tip and the substrate surface is preferably 30 to 300 μm.
According to the die coating method, in order to adjust the thickness of the coating film, the running speed of the lip and the discharge amount of the liquid resin composition from the lip may be adjusted. According to the slit and spin method, The adjustment may be made mainly by the spin rotation speed and the rotation time after slit coating.

  If the coating film is too thick, pattern development becomes difficult and gap adjustment in the liquid crystal cell forming process may be difficult. On the other hand, if the coating film is too thin, it is difficult to increase the pigment concentration. Color expression may be impossible. The thickness of the coating film after drying is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm. The range is as follows.

  The coating film after the colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 The drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter. The reheating drying temperature condition is preferably higher than the preliminary drying temperature. Specifically, it is usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably. Is in the range of 130 ° C. or lower. Moreover, although it depends on the heating temperature, the drying time is usually 10 seconds or longer, preferably 15 seconds or longer, and usually 10 minutes or shorter, preferably 5 minutes or shorter. The higher the drying temperature, the better the adhesion to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, as a drying process of this coating film, you may use the reduced pressure drying method which dries in a reduced pressure chamber, without raising temperature.

  Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating an ultraviolet or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp; Laser light sources such as laser, nitrogen laser, helium cadmium laser, and semiconductor laser are listed. An optical filter can also be used when used by irradiating light of a specific wavelength.

The color filter is a substrate obtained by performing image exposure on the coating film of the colored resin composition with the above light source and then developing with an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. An image can be formed on the top. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
Here, as an alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di- or tri-methylamine , Mono-di- or tri-ethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide ( TMAH), Choline Organic alkali compound may be mentioned. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; and alkylbenzene sulfonic acids. Anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C or higher, especially 15 ° C or higher, more preferably 20 ° C or higher, and usually 50 ° C or lower, especially 45 ° C or lower, more preferably 40 ° C or lower. Is preferred.

The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.
The color filter after development is subjected to heat curing. In this case, the thermosetting treatment conditions are such that the temperature is usually 100 ° C. or more, preferably 150 ° C. or more, and usually 280 ° C. or less, preferably 250 ° C. or less, and the time is 5 minutes or more and 60 minutes or less. Selected by range. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

  In addition to the above-described production method, the color filter in the present invention is (1) a colored resin composition containing a polyimide resin as a solvent, a coloring material, and a binder resin is applied to a substrate, and a pixel image is obtained by an etching method. It can also be produced by a method of forming Also, (2) a method of forming a pixel image directly on a transparent substrate by using a colored resin composition containing a color material as a color ink, and (3) an electrodeposition solution containing the color resin composition containing the color material A method of depositing a colored film on an ITO electrode having a predetermined pattern by immersing the substrate in this electrodeposition solution, and (4) a film coated with a colored resin composition containing a coloring material, It is also produced by a method of forming a pixel image by pasting and peeling, image exposure and development, (5) a method of forming a pixel image with an ink jet printer using a colored resin composition containing a coloring material as a colored ink, etc. can do. As a method for producing the color filter, a method suitable for this is employed according to the composition of the colored resin composition of the present invention.

  Furthermore, when the color filter of the present invention is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is and used as a part of a component such as a color display or a liquid crystal display device. However, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

In the vertical alignment type driving method (MVA mode), ribs may be formed. Also, a column structure (photo spacer) made of photolithography may be formed instead of the bead dispersion type spacer.
[Liquid Crystal Display (Panel)]
The liquid crystal display device according to the present invention has, for example, a structure in which the above-described color filter (hereinafter sometimes referred to as a “color filter substrate”) and a driving substrate made of a thin film transistor (TFT) are opposed to each other through a liquid crystal layer. Can be configured. More specifically, a color filter substrate coated with an alignment film material and subjected to an alignment process and a TFT drive substrate are bonded together via a peripheral sealing material, and a liquid crystal material is injected into the gap, thereby liquid crystal. It can be a display device.

The liquid crystal display device according to the present invention is generally formed by forming an alignment film on the color filter according to the present invention, spraying spacers on the alignment film, and then bonding to a counter substrate to form a liquid crystal cell. The liquid crystal cell is manufactured by injecting liquid crystal and connecting to the counter electrode.
The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film is formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer.
As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable. Further, the bonding gap with the counter substrate varies depending on the use of the liquid crystal panel, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of decompression in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower. The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal.

  In the liquid crystal cell into which liquid crystal is injected, the liquid crystal injection device is completed by sealing the liquid crystal injection port by curing the UV curable resin. The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

[Organic EL display]
When producing an organic EL display using the color filter of the present invention, for example, as shown in FIG. 1, an organic light-emitting body 500 is laminated on the color filter via an organic protective layer 30 and an inorganic oxide film 40. A colored organic EL element can be produced. As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display and an active drive type organic EL display.

Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
<Examples 1-3 and Comparative Examples 1-5>
[1] Synthesis of Dye [1-1] Synthesis Example 1:

5.14 parts by weight of Basic Blue 7 (CI-42595) manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 500 parts by weight of water, and 4.60 parts by weight of sodium 1-naphthalenesulfonate was added with stirring, followed by stirring at room temperature for 1 hour. . The mixture was cooled on ice, and the precipitate was collected by filtration and washed with water. The cake was air-dried and then dried under reduced pressure to obtain 6.11 parts by weight (yield 89%) of Dye A represented by the above structural formula.
[1-2] Synthesis example 2:

An aqueous solution prepared by dissolving 5.14 parts by weight of Basic Blue 7 (CI-42595) manufactured by Tokyo Chemical Industry Co., Ltd. in 400 parts by weight of water and dissolving 3.00 parts by weight of sodium 4-phenylaminobenzenesulfonate in 100 parts by weight of water. In addition, after stirring at room temperature for 1 hour, the precipitate was collected by filtration and dried under reduced pressure to obtain 5.22 parts by weight of dye B represented by the above structural formula (yield 72%).
[2] Synthesis of binder resin [2-1] Synthesis example 3:
Synthesis of Binder Resin a 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 20 parts by weight of styrene, 57 parts by weight of glycidyl methacrylate and 82 parts by weight of a monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and the mixture was further stirred at 120 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were added to 27 parts by weight of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 52 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 120 ° C. for 3.5 hours. The binder resin a thus obtained had a weight average molecular weight Mw measured by GPC of about 15,000. The structure of the binder resin a was as shown below (polymer compound containing the following four types of repeating units).

[3] Preparation of colored resin composition
[3-1] Preparation of dye-based composition (Examples 1 to 3 and Comparative Examples 1 to 4)
Table 1 shows the dyes (pigments) contained in Examples 1 to 3 and Comparative Examples 1 to 4.

Other components were mixed with each of the dyes and the binder resin described in Table-2 to prepare a colored composition represented in Table-2. In mixing, the mixture was stirred for 1 hour or more until the dye was sufficiently dissolved, and finally filtered through a 5 μm piece filter to remove foreign matters.

[3-2] Preparation of pigment-based composition (Comparative Example 5)
CI Pigment Blue 15: 6 10.00 parts by weight as a color material, 1.36 parts by weight of CI Pigment Violet 23, 57.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and Disperbic 2000 manufactured by BYK Chemie Company as a dispersant. A stainless steel container was filled with 02 parts by weight and 215.7 parts by weight of zirconia beads having a diameter of 0.5 mm, and dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion.

  Other components were mixed with the obtained pigment dispersion and the binder resin shown in Table-3 to prepare colored compositions shown in Table-3.

[4] Spectral characteristics and heat resistance evaluation Each colored resin composition is applied to a glass substrate cut into 5 cm square by spin coating so as to have a dry film thickness of 1.8 μm, dried under reduced pressure, and then hot plate. 80 ° C 3 above
Pre-baked for a minute. Thereafter, the entire surface was exposed at an exposure amount of 60 mJ / cm ² , and then the spectral transmittance was measured with a spectrophotometer U-3310 manufactured by Hitachi, Ltd., and the chromaticity (C light source) in the XYZ color system was calculated. The results are shown in Table-4 and Table-5.

The colored resin compositions of the examples have excellent spectroscopic properties compared to the colored resin compositions (Comparative Examples 1 to 4) containing a dye having a similar structure and the conventional pigment dispersion colored resin composition (Comparative Example 5). It can be seen that it has characteristics. In particular, the luminance (Y) at the same chromaticity coordinate shows an improvement of 20% or more compared to the conventional pigment system.
Moreover, in comparison with the dye having the similar structure (Comparative Examples 2 to 4), the colored resin composition described in the Examples expresses a deep blue color at the same dye concentration and the same film thickness. Since the colored resin compositions of Examples 2 to 4 only represent light blue-green (see chromaticity data in Table 5), it can be said that the colored resin compositions exhibit an overwhelming advantage in terms of color reproducibility. .
Subsequently, Examples 1 to 3 and Comparative Example 1 having good spectral characteristics among the above substrates were baked at 150 ° C., 180 ° C., and 200 ° C. for 30 minutes in a clean oven, and then spectral transmission was performed as described above. The rate was measured and the color difference (ΔE * ab) was measured. The results are shown in Table-6. It turns out that the colored resin composition of an Example has high heat resistance compared with the composition of a comparative example, and especially Examples 1 and 2 are excellent.

Next, the coated substrate was combined with an organic electroluminescence device to measure chromaticity.
[5] Preparation of organic electroluminescent device The organic electroluminescent device shown in FIG. 2 was prepared by the following method.
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate 1 having a thickness of 150 nm (sputtered film; sheet resistance 15Ω) is patterned into a 2 mm wide stripe using ordinary photolithography and hydrochloric acid etching. Thus, an anode 2 was formed. The patterned ITO substrate was cleaned in the order of ultrasonic cleaning with acetone, water with pure water, and ultrasonic cleaning with isopropyl alcohol, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning. Subsequently, 9,9-bis [4- (N, N-bisnaphthylamino) phenyl] -9H-fluorene (LT-N121, manufactured by Luminescent Technology) shown in Formula IX is used as the hole transport layer 3 in a crucible temperature. Deposition rate is 0 at 285 ° C to 310 ° C
. Lamination was performed at a thickness of 40 nm at 1 nm / second. The degree of vacuum at the time of deposition was 1.7 × 10 ⁻⁴ Pa.

Next, as the light-emitting layer 4, 2,2′-diperylenyl-9,9′-spirobifluorene (LT-N428, manufactured by Luminescent Technology) represented by Formula X and Formula X
2,7-bis [9,9′-spirobifluorenyl] -9,9′-spirobifluorene (LT-N628, manufactured by Luminescent Technology) shown in I was co-evaporated under the following conditions.

(Evaporation conditions for light emitting layer)
LT-N428 crucible temperature 320 ° C-330 ° C
LT-N628 crucible temperature 450 ° C-455 ° C
The vapor deposition rate of LT-N428 was 0.1 nm / sec. The vapor deposition rate of LT-N628 was 0.05 nm / sec. The degree of vacuum at the time of deposition was 1.7 to 1.9 × 10 ⁻⁴ Pa. Subsequently, 1,3-bis [2- (2,2′-bipyridinyl) -1,3,4-oxadiazoyl] -benzene (LT-N820) represented by Formula XII as the electron transport layer 5 is formed on the light-emitting layer 4. , Manufactured by Luminescent Technology) with a film thickness of 30 nm. At this time, the crucible temperature of LT-N820 is controlled in the range of 255 ° C. to 260 ° C., the deposition rate is controlled in the range of 0.08 nm / second to 0.1 nm / second, and the degree of vacuum during deposition is 1.2 × 10 ⁻⁴ Pa. Met.

In addition, the substrate temperature at the time of vacuum-depositing said positive hole transport layer 3, the light emitting layer 4, and the electron carrying layer 5 was kept at room temperature. Here, the element formed up to the electron transport layer 5 was once taken out from the vacuum deposition apparatus into the atmosphere. Next, a stripe shadow mask having a width of 2 mm was brought into close contact with the element so as to be orthogonal to the ITO stripe of the anode 2 as a mask for cathode vapor deposition. Subsequently, this element was placed in another vacuum vapor deposition apparatus and evacuated until the degree of vacuum in the vacuum vapor deposition apparatus was 2.3 × 10 ⁻⁵ Pa or less, as in the case where the organic layer was formed. Next, as the cathode 9, first, lithium fluoride (LiF) was deposited using a molybdenum boat at a deposition rate of 0.008 nm / second to 0.01 nm / second at a degree of vacuum of 3.7 × 10 ⁻⁶ Pa. The film was formed on the electron transport layer 5 with a film thickness of 5 nm. Subsequently, similarly, the aluminum was heated by a molybdenum boat, the film thickness at a deposition rate of 0.1 nm / sec to 0.2 nm / sec, the vacuum degree ^{2.7 × 10 -6 Pa~2.5 × 10 -6} Pa A cathode 6 was completed by forming an aluminum layer of 80 nm. When forming the above two-layer cathode 6, the substrate temperature during vapor deposition was kept at room temperature. As described above, an organic electroluminescent device having a light emitting area portion having a size of 2 mm × 2 mm was prepared. The presence or absence of light emission and the color of light emitted when a voltage of 6 V was applied to the device were evaluated. The maximum wavelength of the EL emission spectrum at this time was 436 nm, and the CIE chromaticity coordinates (CIE chromaticity coordinates when the front luminance was 10 to 1000 cd / m ² ) were (0.16, 0.15).

[6] Spectral characteristics evaluation The chromaticity was measured by combining the organic electroluminescent light emitting device and the coated substrates of Examples 1 to 3 and Comparative Examples 1 to 5. The results are shown in Table-7.

  Similarly to the comparison with the C light source, it can be seen that the colored resin compositions described in the examples also have high spectral characteristics in the comparison when the organic electroluminescent device is used as the light source.

It is an example of the cross-sectional schematic diagram of the organic EL element provided with the blue color filter of this invention. It is a cross-sectional schematic diagram which shows the structure of the organic electroluminescent light emitting element created in the Example.

Explanation of symbols

1, 10 Transparent support substrate 2, 50 Transparent anode 3, 52 Hole transport layer 4, 53 Light emitting layer 5, Electron transport layer 6, 55 Cathode 100 Organic EL element 20 Blue color filter 30 Organic protective layer 40 Inorganic oxide film 500 Organic light emission Body 51 hole injection layer 54 electron injection layer

Claims (8)

A colored resin composition for a color filter, which contains (a) a binder resin and (b) a solvent and dissolves a triarylmethane dye represented by the following general formula (I).

(In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represents an alkyl group, R ⁵ represents an alkyl group or an aryl group which may have a substituent, and X ⁻ represents Cl ^- or ArSO ₃ ^- the .Ar represents an aromatic ring showing, aromatic ring may be substituted by an amino group which may have a substituent).   The colored resin composition for a color filter according to claim 1, further comprising (d) a pigment.   The colored resin composition for a color filter according to claim 1 or 2, further comprising (c) a monomer.   The colored resin composition for a color filter according to any one of claims 1 to 3, further comprising (e) a photopolymerization initiation system and / or a thermal polymerization initiation system.   The colored resin composition for a color filter according to any one of claims 1 to 4, wherein the compound represented by the general formula (I) is dissolved in 1 to 50% by weight in the total solid content.   The color filter which has a pixel formed using the colored resin composition for color filters as described in any one of Claims 1 thru | or 5.   An organic EL display formed using the color filter according to claim 6.   A liquid crystal display device formed using the color filter according to claim 6.

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