KR20130111189A - Colored photosensitive composition, color filter, method of producing the same, and display device - Google Patents

Abstract

PURPOSE: A tinted photosensitive composition, a color filter, a manufacturing method thereof, and an indicator are provided to form a tinted layer with enhanced heat resistance, luminance and contrast. CONSTITUTION: A tinted photosensitive composition comprises blue pigment; dye with different skeleton from the blue pigment; and a polymerizable compound. 15 mass% or more of the pigment is absorbed on the surface of the blue pigment. A manufacturing method of the color filter comprises the following steps: forming a tinted layer by adding the tinted photosensitive composition to a supporting body; exposing the formed tinted layer in a pattern form; and forming a tinted pattern by developing the tinted layer after exposure.

Description

Colored photosensitive composition, color filter and manufacturing method thereof, and display device {COLORED PHOTOSENSITIVE COMPOSITION, COLOR FILTER, METHOD OF PRODUCING THE SAME, AND DISPLAY DEVICE}

The present invention relates to a colored photosensitive composition, a color filter, a manufacturing method thereof, and a display device.

The pigment dispersion method is known as one of the methods of preparing the coloring photosensitive composition used for manufacture of the color filter used for a liquid crystal display device or a solid-state image sensor (CCD, CMOS, etc.).

This pigment dispersion method is a method of producing a color filter by photolithography using a colored photosensitive composition in which pigments are dispersed in various photosensitive compositions. Since this is patterned by the photolithography method, it is considered to be a preferable method for producing a color filter with high positional precision, a large screen, and a high quality. When manufacturing a color filter by the pigment dispersion method, a coloring photosensitive composition is apply | coated with a spin coater, a roll coater, etc., and a coating film is formed, A coloring pattern is formed by exposing and developing the said coating film, and this operation is repeated for each color. By doing so, a color filter is obtained. As a coloring photosensitive composition, the blue coloring photosensitive composition for color filters containing a phthalocyanine type pigment is known, for example (for example, refer Unexamined-Japanese-Patent No. 3387541).

In recent years, performance demands on color filters have become more and more stringent, and in particular, color and luminance are emphasized.

In response to such a situation, a technique of using a dye instead of a pigment is conventionally proposed (see, for example, Japanese Patent No. 3387541, Japanese Patent Application Laid-Open No. 2008-292970, and Japanese Patent Publication No. 2009-86375). ). However, dyes are generally known to be inferior in heat resistance to pigments, and further improvement is required in order to sufficiently exhibit the performance of the dyes.

For this reason, a technique of using a dye and a pigment together has been developed. For example, although water-based inkjet recording inks using pigments adsorbed with dyes have been proposed (see, for example, Japanese Patent Application Laid-Open No. 9-151344 and Japanese Patent No. 4167053). It is not tolerable and better technology development is desired. Moreover, it is also proposed to make a pigment | dye composition which disperse | distributes a pigment with a polymeric dispersing agent, and contains the dye which is not adsorb | sucked to the surface of a pigment, and provides a coloring photosensitive composition using this (for example, Unexamined-Japanese-Patent No. 2011-). See 178865.).

Moreover, as a method of preparing a coloring photosensitive composition using a pigment and dye, the method of mixing powder dye directly into the pigment dispersion which disperse | distributed a pigment is considered. In this method, when the solid concentration in the composition is high or when the mass ratio of the dye to the pigment is large, when the dye is directly added to the pigment dispersion, the pigment is dispersed in the process of dissolving the dye in the solvent in the stirring and dissolving step after the addition. There exists a tendency for a state to change and the dispersibility and dispersion stability of a pigment deteriorate.

Further, in this method, it sometimes takes a long time to dissolve the dye as a powder, the dye does not completely dissolve, or the dye is difficult to uniformly mix. In addition, there is a concern that it is difficult to confirm that the dye is dissolved, and there is a problem in manufacturing.

The coloring photosensitive composition obtained by these methods mentioned above is a thing which cannot fully respond to the request | requirement to the color filter which is high in heat resistance and can display a high quality image, and further improvement is desired.

The present invention has been made in view of the above situation. That is, an object of the present invention is to provide a colored photosensitive composition capable of forming a colored layer having good heat resistance, high luminance and high contrast when a colored layer such as a color filter is formed.

The present invention also provides a color filter capable of displaying an image having high brightness and high contrast, a method of manufacturing the same, and a display device capable of displaying good image quality including the color filter, using the colored photosensitive composition. The task is to provide.

The above object of the present invention can be achieved by the following means.

<1> (A) blue pigment, (B) dye which has a parent skeleton different from the said blue pigment, and (C) polymeric compound, and 15 mass% or more of said (B) dye is said (A) It is adsorbed by the surface of a blue pigment, The coloring photosensitive composition characterized by the above-mentioned.

<2> The colored photosensitive composition as described in <1> containing the dispersion composition obtained by disperse | distributing the said (A) blue pigment and the said (B) dye in situ.

<3> When the said dispersion composition makes Ci the density | concentration of the said (B) dye in the dispersion composition of the initial stage of dispersion, and the density | concentration of the said (B) dye in the dispersion composition after completion | finish of dispersion is Cf> It is a dispersion composition which satisfy | fills the relationship of Cf, The coloring photosensitive composition characterized by the above-mentioned.

<4> The structure according to any one of <1> to <3>, wherein the structure represented by the following general formula (I) is a metal complex compound coordinated with a metal atom or a metal compound. Coloring photosensitive composition.

In general formula (I), R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , and R <^6> represent a hydrogen atom or a monovalent substituent each independently, R <^7> represents a hydrogen atom, a halogen atom, an alkyl group, An aryl group or a heterocyclic group is shown.

<5> The dispersion composition according to any one of <1> to <4>, which comprises dispersing the obtained color material mixture after premixing the (A) blue pigment and the (B) dye. The coloring photosensitive composition to make.

<6> The colored photosensitive composition according to any one of <1> to <5>, further comprising (D) a photopolymerization initiator.

<7> The coloring photosensitive composition of any one of <1>-<6> which further contains (E) alkali-soluble binder.

<8> The color filter produced using the coloring photosensitive composition in any one of <1>-<7>.

<9> The colored layer formation process of providing the coloring photosensitive composition in any one of <1>-<7> on a support body, and forming a colored layer, the exposure process of exposing the formed colored layer in a pattern form, and exposure It has a developing process of developing a subsequent coloring layer and forming a coloring pattern, The manufacturing method of the color filter characterized by the above-mentioned.

<10> Display apparatus provided with the color filter as described in <8> or the manufacturing method as described in <9>.

<11> A method for producing a colored photosensitive composition, wherein the (A) blue pigment and (B) dye are dispersed to prepare a dispersion composition, and a colored photosensitive composition is prepared using the dispersion composition.

<12> The said (A) blue pigment and (B) dye are mixed, the color material composition is prepared, the said color material composition is disperse | distributed, the dispersion composition is prepared, and the coloring photosensitive composition is prepared using the said dispersion composition. The manufacturing method of the coloring photosensitive composition to make.

In the present invention, a blue pigment and a dye (having a mother skeleton different from the pigment) are used as the colorant, and a part of the dye is adsorbed on the surface of the blue pigment, and the surface of the blue pigment is assumed to be coated with dye molecules. do. Since the dye adheres to the pigment surface by adsorbing to the pigment, the molecular motion of the dye is suppressed, and even when heated, the dye is considered to be decomposed, and the colored layer formed by using the colored photosensitive composition of the present invention is heated. It is thought that discoloration may be suppressed even by. On the other hand, since the blue pigment is coated with a dye, even if the blue pigment becomes fine particles in dispersion or the like, the coated dye acts as a protective colloid, so that the dispersed state of the pigment is stably maintained, whereby the dispersion stability of the blue pigment is improved to improve contrast and the like. It is guessed that this will increase.

Generally, only a dye (dye powder or dye solution dissolved in an organic solvent) is mixed into a pigment dispersion, and the dye is not adsorbed to the pigment, or the adsorption rate is small even if adsorbed. On the other hand, the dispersion composition which directly disperse | distributed a blue pigment and dye, or the color material mixture containing a blue pigment and dye is previously prepared, and the coloring photosensitive composition is prepared using the dispersion composition which disperse | distributed this color material mixture. Since the adsorption rate of a dye to the pigment surface of a coloring photosensitive composition becomes large, it is guessed that the obtained colored layer was high in heat resistance and obtained high contrast.

(Effects of the Invention)

According to this invention, when colored layers, such as a color filter, are formed, the coloring photosensitive composition which can form the colored layer with favorable heat resistance, high brightness, and high contrast can be provided.

Further, according to the present invention, a color filter manufactured by using the coloring photosensitive composition, capable of displaying an image having high brightness and high contrast, a method of manufacturing the same, and a display device capable of displaying good image quality with the color filter Can be provided.

The coloring photosensitive composition of this invention contains (A) blue pigment, (B) dye which has a mother skeleton different from the said blue pigment (henceforth "specific dye" suitably), and (C) polymeric compound 15 mass% or more of a specific dye is adsorb | sucked to the surface of the said (A) blue pigment, It is characterized by the above-mentioned.

In addition, although the adsorption rate of the specific dye in the coloring photosensitive composition to the surface of the blue pigment is 15 mass% or more of a specific dye, it is preferable that it is 20 mass% or more. The upper limit of the adsorption amount is better from the gist of the present invention, but it is practically 90 mass% or less because excessively coating the pigment surface with a dye may inhibit the adsorption of the dispersant.

In the present specification, the symbol &quot; ~ &quot; indicates the range of the lower limit value to the upper limit value. In addition, in the description of group in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent.

In addition, in this specification, "the total solid of a coloring photosensitive composition" means the sum total of the remaining component except the organic solvent from the all components which comprise a coloring photosensitive composition.

In addition, in this invention, the adsorption rate of the dye to the pigment surface is centrifuged by dispersing the dispersion composition with a ultracentrifuge (manufactured by Hitachi Koki Co., Ltd.) 50000 rpm, and extracting the amount of dye in the supernatant obtained by extracting a supernatant liquid containing a glass component. Measured by HPLC, defined as the dye adsorption rate obtained by the following formula, expressed in%. The ultracentrifugal separator used for the centrifugal treatment is CS150GX (manufactured by Hitachi Koki Co., Ltd.). The centrifugal capacity is 1 g and the centrifugal time is generally about 1 to 6 hours (although it may vary depending on the sample).

<Coloring Photosensitive Composition>

Below, the essential component and optional component which comprise the coloring photosensitive composition of this invention are demonstrated.

The coloring photosensitive composition of this invention has (A) blue pigment, (B) specific dye, and (C) polymeric compound as an essential component.

[(A) Blue Pigment]

The coloring photosensitive composition of this invention contains (A) blue pigment, As a blue pigment, both a blue organic pigment and a blue inorganic pigment can be used, but a blue organic pigment is preferable.

As a blue organic pigment, it is C.I. Changed Cl substituent of Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 to OH , And 80 are preferable, and among these, CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, and 66 are preferred.

In addition, considering that the average primary particle diameter of the blue pigment is preferably high transmittance, it is preferable to select a pigment having a small particle size and a small particle size as much as possible. In particular, in consideration of handling properties, the blue pigment is preferably a pigment having an average primary particle diameter of 0.01 µm to 0.3 µm, more preferably 0.01 µm to 0.15 µm. The average primary particle diameter of a blue pigment being in the said range is effective at high transmittance | permeability, favorable color characteristic, and forming a high contrast color filter.

The average primary particle size is obtained by observing the particles by SEM or TEM, measuring 100 particle sizes at the portion where the particles do not aggregate, and calculating the average value of the measured particle sizes.

In the coloring photosensitive composition of this invention, organic pigments other than a blue pigment and an inorganic pigment can also be used further for coloring, etc. as needed.

As pigments other than the blue pigment which can be used further, the following organic pigments are mentioned, for example. However, in this invention, the pigment which can be used further is not limited to these.

C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214

C.I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73

C.I. Pigment Green 7, 10, 36, 37, 58

C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42

C.I. Pigment Brown 25, 28

C.I. Pigment Black 1

Among these, the following can be mentioned as an organic pigment which can be used preferably.

C.I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185

C.I. Pigment Orange 36, 71

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

C.I. Pigment Violet 19, 23, 32

C.I. Pigment Green 7, 36, 37, 58

C.I. Pigment Black 1

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, and the And complex oxides of metals.

[(B) Specific Dye]

The coloring photosensitive composition of this invention contains dye (= specific dye) which has a mother skeleton different from (A) blue pigment.

A parent skeleton is a structural part which characterizes the structure and color of a dye, for example, a structure called phthalocyanine, a pyrromethene, an anthraquinone.

There is no restriction | limiting in particular if a specific dye is a dye which has a parent skeleton different from a blue pigment, From a viewpoint of the chemical structure, a pyrimethene type, a pyrazole azo type, an alino azo type, a triphenylmethane type, an anthraquinone type, an anthrapyridone type, Dye such as benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran and indigo have.

As these specific examples, For example, Unexamined-Japanese-Patent No. 64-90403, Unexamined-Japanese-Patent No. 64-91102, Unexamined-Japanese-Patent No. 1-94301, Unexamined-Japanese-Patent No. 6-11614, Japan patent No. 2592207, US Pat. No. 4,808,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6 -51115, Japanese Patent Laid-Open No. 6-194828, Japanese Patent Laid-Open No. 8-211599, Japanese Patent Laid-Open No. 4-249549, Japanese Patent Laid-Open No. 10-123316, Japanese Patent Laid-Open No. 11 -302283, Japanese Patent Laid-Open No. 7-286107, Japanese Patent Laid-Open No. 2001-4823, Japanese Patent Laid-Open No. 8-15522, Japanese Patent Laid-Open No. 8-29771, Japanese Patent Laid-Open No. 8- 146215, Japanese Patent Laid-Open No. 11-343437 Japanese Patent Laid-Open No. 8-62416, Japanese Patent Laid-Open No. 2002-14220, Japanese Patent Laid-Open No. 2002-14221, Japanese Patent Laid-Open No. 2002-14222, Japanese Patent Laid-Open No. 2002-14223, Japanese Patent The pigment | dye described in Unexamined-Japanese-Patent No. 8-302224, Unexamined-Japanese-Patent No. 8-73758, Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531, etc. are mentioned.

(Dipyrromethene-Based Metal Complex Compound)

Among these dyes, as a specific dye of the colored photosensitive composition of the present invention, a metal complex compound in which a structure represented by the following general formula (I) is distributed to a metal atom or a metal compound (hereinafter, suitably referred to as "dipyrromethene metal complex" Compound ").

The dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated with a metal atom or a metal compound will be described in detail.

In general formula (I), R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , and R <^6> represent a hydrogen atom or a monovalent substituent each independently, R <^7> represents a hydrogen atom, a halogen atom, an alkyl group, An aryl group or a heterocyclic group is shown.

As the monovalent substituent (hereinafter may be referred to as substituent R), a halogen atom (for example, a fluorine atom, a chlorine atom, or a bromine atom), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms) It is a linear, branched, or cyclic alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group , Dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably 2 to 48 carbon atoms, more preferably 2 carbon atoms) It is an alkenyl group of -18, For example, a vinyl group, an allyl group, 3-buten- 1-yl group, an aryl group (preferably C6-C48, More preferably, it is an C6-C24 aryl group, an example) For example, a phenyl group, a naphthyl group, a heterocyclic group (preferably C1-C32, More preferably, carbon) Heterocyclic group of the number 1-18, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl Group, 1-pyrazolyl group, benzotriazol-1-yl group, silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms), for example trimethylsilyl group and triethyl Silyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably C1-C48, more preferably C1-C1) If it is an alkoxy group of -24, for example, a methoxy group, an ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxy group, dodecyloxy group, and a cycloalkyloxy group, for example Cyclopentyloxy group, cyclohexyloxy group),

Aryloxy group (preferably C6-C48, more preferably C6-C24 aryloxy group, for example, a phenoxy group, 1-naphthoxy group), heterocyclic oxy group (preferably C1-C1) 32, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, for example, a 1-phenyltetrazol-5-oxy group, a 2-tetrahydropyranyloxy group), and a silyloxy group (preferably 1 to 1 carbon atom). 32, More preferably, it is a C1-C18 silyloxy group, For example, a trimethylsilyloxy group, t-butyl dimethyl silyloxy group, a diphenylmethyl silyloxy group), an acyloxy group (preferably C2-C20) 48, more preferably an acyloxy group having 2 to 24 carbon atoms, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), and an alkoxycarbonyloxy group (preferably 2 to 24 carbon atoms). 48, More preferably, it is a C2-C24 alkoxycarbonyloxy group. For example, if it is an ethoxycarbonyloxy group, t-butoxycarbonyloxy group, and a cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably Preferably it is a C7-C32, More preferably, it is a C7-C24 aryloxycarbonyloxy group, For example, a phenoxycarbonyloxy group, Carbamoyloxy group (preferably C1-C48), More preferably Is a carbamoyloxy group having 1 to 24 carbon atoms, for example, an N, N-dimethylcarbamoyloxy group, an N-butylcarbamoyloxy group, an N-phenylcarbamoyloxy group, or an N-ethyl-N-phenylcarba Moyloxy group), sulfamoyloxy group (preferably sulfayloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-diethyl sulfamoyloxy group and N-propyl sulfamoyloxy group) ,

Alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylsulfonyloxy group, hexadecylsulfonyloxy group, cyclohexylsulfonyloxy group), aryl Sulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, a phenylsulfonyloxy group) and an acyl group (preferably 1 to 48 carbon atoms) Is an acyl group having 1 to 24 carbon atoms, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably 2 to 48 carbon atoms), more preferably Is an alkoxycarbonyl group having 2 to 24 carbon atoms, for example, a methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbon An aryloxycarbonyl group (preferably a C7-32, more preferably an aryloxycarbonyl group having 7-24 carbon atoms, for example, a phenoxycarbonyl group), a carbamoyl group (preferably 1-48 carbon atoms) Preferably it is a C1-C24 carbamoyl group, For example, a carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N- dibutyl carbamoyl group , N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably having 32 or less carbon atoms, more preferably An amino group having 24 or less carbon atoms, for example, an amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, cyclohexylamino group),

An anilino group (preferably a 6-32 carbon atoms, more preferably a 6-24 anilin group), for example, an anilino group, an N-methylanilino group, and a heterocyclic amino group (preferably C1-C1). 32, more preferably 1 to 18 heterocyclic amino groups, for example, 4-pyridylamino group, carbonamide group (preferably 2 to 48 carbon atoms, more preferably 2 to 24 carbonamide groups), For example, acetamide group, benzamide group, tetradecanamide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferably C1-C32, more preferably C1-C24 ureido group) For example, it is a ureido group, N, N- dimethyl ureido group, N-phenyl ureido group, an imide group (preferably 36 or less carbon atoms, More preferably, it is an imide group of 24 or less carbon atoms, for example, N- Succinimide group, N-phthalimide group), alkoxy Carbonylamino group (preferably alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, Octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms), for example Phenoxycarbonylamino group) and sulfonamide group (preferably sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), for example, methane sulfonamide group, butane sulfonamide group, and benzene sulfonamide group. , Hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably C1-C24, more preferably C1-C24 sulfamoylamino group) For example, N, N-dipropyl sulfamoylamino group, N-ethyl-N-dodecyl sulfamoylamino group, an azo group (preferably C1-C32, More preferably, it is a C1-C24 azo group, for example) Phenyl azo group, 3-pyrazolyl azo group),

Alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (Preferably an arylthio group having 6 to 48 carbon atoms, more preferably a 6 to 24 carbon atoms, for example, a phenylthio group), a heterocyclic thi group (preferably 1 to 32 carbon atoms), and more preferably 1 carbon atom. It is a heterocyclic thi group of -18, For example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyl tetrazolylthio group), an alkylsulfinyl group (preferably C1-C32), More preferably, Is an alkylsulfinyl group having 1 to 24 carbon atoms, for example, a dodecanesulfinyl group and an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms), for example, phenyl Sulfinyl group), alkylsulfonyl group (preferably having 1 to 48 carbon atoms) Preferably it is a C1-C24 alkylsulfonyl group, For example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octyl Sulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenylsulfonyl group and 1-naphthylsulfonyl group), Sulfamoyl groups (preferably sulfamoyl groups having 32 or less carbon atoms, more preferably 24 or less carbon atoms, for example, sulfamoyl groups, N, N-dipropylsulfamoyl groups, and N-ethyl-N-dodecylsulfamo) Diary, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group, sulfo group, phosphonyl group (preferably phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms). For example, phenoxy phosphonyl group, octyloxy phosphonyl group, phenyl phosphonyl ) And a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, diethoxyphosphinoylamino group and dioctyloxyphosphinoylamino group). .

When the monovalent group mentioned above is group which can be further substituted, you may further substitute by any one of each group mentioned above. In addition, when it has two or more substituents, those substituents may be same or different.

In general formula (I), R <^1> and R <^2> , R <^2> and R <^3> , R <^4> and R <^5> , and R <^5> and R <^6> combine with each other independently, and are a 5-, 6-, or 7-membered ring. May be formed. In addition, the ring formed includes a saturated ring or an unsaturated ring. Examples of the 5-membered, 6-membered or 7-membered ring or the unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, A cyclopentene ring, a cyclohexane ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazin ring, and preferred examples thereof include a benzene ring and a pyridine ring.

In addition, when the 5-membered, 6-membered, and 7-membered ring formed is a group which can be further substituted, it may be substituted with any one of the above substituents R, and when substituted with two or more substituents, those substituents may be the same or different. good.

In the formula (I), when R ⁷ is a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, these preferred ranges thereof are the halogen atom, alkyl group, aryl group, or heterocyclic group as R ¹ to R ⁶ described above. It is equal to the preferred range of.

In general formula (I), as said R <^1> and R <^6> , an alkylamino group, an arylamino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, and a sulfonamide group are preferable among the said, and a carbonamide group and a ureido group , An alkoxycarbonylamino group and a sulfonamide group are more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group and a sulfonamide group are more preferable, and a carbonamide group and a ureido group are particularly preferable.

In general formula (I), as said R <^2> and R <^5> , an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group are preferable among the said, , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, and alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, and carbon Bamoylsulfonyl group is more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, and carbamoyl group are especially preferable.

In general formula (I), as said R <^3> and R <^4> , a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group are preferable among the above, More preferably, it is substituted or no Substituted alkyl group, substituted or unsubstituted aryl group.

In general formula (I), when said R <^3> and R <^4> represents an alkyl group, Preferably it is a C1-C12 linear, branched or cyclic substituted or unsubstituted alkyl group, More specifically, For example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, t-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and Benzyl group, More preferably, they are a C1-C12 branched chain or a cyclic substituted or unsubstituted alkyl group, More specifically, For example, an isopropyl group, a cyclopropyl group, i-butyl group, t-butyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group are mentioned, More preferably, they are a C1-C12 secondary or tertiary substituted or unsubstituted alkyl group, More specifically, Examples For example, isopropyl group, cyclopropyl group, i-butyl group, t-butyl group , A cyclobutyl group, and a cyclohexyl group are mentioned.

In general formula (I), when said R <^3> and R <^4> represents an aryl group, Preferably, a substituted or unsubstituted phenyl group and a substituted or unsubstituted naphthyl group are mentioned, More preferably, It is a substituted or unsubstituted phenyl group.

As said heterocyclic group when R <^3> and R <^4> represents a heterocyclic group, Preferably, a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted 3-pyridyl group, Substituted or unsubstituted 2-pyridyl group, substituted or unsubstituted 2-furyl group, substituted or unsubstituted 2-pyrimidinyl group, substituted or unsubstituted 2-benzothiazolyl group, substituted or unsubstituted 1- An imidazolyl group, a substituted or unsubstituted 1-pyrazolyl group, a substituted or unsubstituted benzotriazol-1-yl group, and more preferably a substituted or unsubstituted 2-thienyl group, substituted or unsubstituted. A substituted 4-pyridyl group, a substituted or unsubstituted 2-furyl group, a substituted or unsubstituted 2-pyrimidinyl group, and a substituted or unsubstituted 1-pyridyl group.

Next, the metal atom or metal compound which forms a dipyrromethene type metal complex compound is demonstrated.

The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and includes divalent metal atoms, divalent metal oxides, divalent metal hydroxides, or divalent metal chlorides. For example, AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , and the like are used in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, , GeCl ₂ and the like, metal oxides such as TiO ₂ and VO, and metal hydroxides such as Si (OH) ₂ .

Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO is preferable from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex. Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferred, and Fe, Zn, Cu, Co, B, or VO (V = O) is most preferred. . Among these, Zn is especially preferable.

The preferable form of the dipyrromethene type metal complex compound which has a structure in which the compound represented by the said general formula (I) is coordinated with a metal atom or a metal compound is shown below. Namely, in general formula (I), R ¹ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, Heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, An azo group, an alkylthio group, an arylthio group, a heterocyclic thi group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, and R ² and R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an alkenyl group , Aryl group, heterocyclic group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonyl Mino group, a sulfonamide group, an azo group, an alkylthio, arylthio, coming heterocycle tea, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group represents a group, R ³ and R ⁴ are each independently a hydrogen atom, a halogen Atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, alinino group, carbon Amide group, ureido group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thi group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, or phosphinoylamino group R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and a metal atom or a metal compound represents Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO , B, or VO.

The more preferable aspect of a dipyrromethene type metal complex compound is shown below. That is, in the general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, a hetero Represented by ring amino group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group, R ² and Each R ⁵ independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imide group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfonate represents a sulfamoyl group, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carbon amido Group, a ureido group, an imide group, alkoxycarbonylamino group, sulfonamide group, alkylthio group, arylthio group, come heterocycle tea, alkylsulfonyl group, arylsulfonyl represents a group, or a sulfamoyl group, R ⁷ is a hydrogen atom , A halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and a metal atom or a metal compound may be Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO.

A preferred embodiment of the dipyrromethene-based metal complex compound wherein the compound represented by the general formula (I) is assigned to a metal atom or a metal compound is a complex compound represented by the following general formula (I-3).

In the general formula (I-3), R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or Heterocyclic group is shown. R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. And Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group.), An oxygen atom, or a sulfur atom. . Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, a sulfur atom, or a carbon source Represents a ruler. X ⁵ represents a group bondable with Ma and a represents 0, 1, or 2. R ⁸ and Y ¹ may be bonded to form a 5-membered, 6-membered or 7-membered ring, and R ⁹ and Y ² may be bonded to form a 5-membered, 6-membered or 7-membered ring good.

General formula (I-3) of the R ² ~R ^5, and R ⁷ is R ² ~R ^5, and R ⁷ and the consent of the general formula (I), as a preferred form.

Ma in general formula (I-3) represents a metal or a metal compound, and the compound represented by the said general formula (I) is synonymous with the metal atom or the metal compound in the complex arrange | positioned to a metal atom or a metal compound, The preferred range is also the same.

In general formula (I-3), R <^8> and R <^9> is respectively independently an alkyl group (preferably C1-C36, More preferably, they are a linear, branched, or cyclic alkyl group of 1-12, for example, Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-a Monovalent group), alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms), for example, a vinyl group, allyl group, and 3-buten-1-yl group, and an aryl group (preferably Is an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, for example, a phenyl group or a naphthyl group, a heterocyclic group (preferably 1 to 24 carbon atoms, more preferably a 1 to 12 heterocyclic group), For example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyra Aryl group, benzotriazol-1-yl group, alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms), for example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, Hexyloxy group, 2-ethylhexyloxy group, dodecyloxy group, cyclohexyloxy group), aryloxy group (preferably C6-C24, more preferably 1-18 aryloxy group, For example, phenoxy Time period, naphthyloxy group), alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms), for example, methylamino group, ethylamino group, propylamino group, butylamino group, hexylamino group, 2- Ethylhexylamino group, isopropylamino group, t-butylamino group, t-octylamino group, cyclohexylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-dibutylamino group, N-methyl- N-ethylamino group), arylamino group (preferably carbon number) It is 6-36, More preferably, it is 6-18 arylamino group, For example, a phenylamino group, a naphthylamino group, N, N- diphenylamino group, N-ethyl-N-phenylamino group, or a heterocyclic amino group (preferably Preferably it is a C1-C24, more preferably 1-12 heterocyclic amino group, for example, 2-aminopyrrole group, 3-aminopyrazole group, 2-aminopyridine group, 3-aminopyridine group).

In the general formula (I-3), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group represented by R ⁸ and R ⁹ may be further substituted. In the case, it may be substituted by any one of the said substituents R, and when substituted by two or more substituents, those substituents may be same or different.

In General Formula (I-3), X ³ and X ⁴ each independently represent NRa, an oxygen atom, or a sulfur atom. Ra is a hydrogen atom, an alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl) , Isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 2 carbon atoms) 24, More preferably, it is an alkenyl group of 2-12, For example, a vinyl group, an allyl group, 3-buten-1-yl group, an aryl group (preferably C6-C36, More preferably, 6-18) Aryl group, for example, a phenyl group, a naphthyl group, a heterocyclic group (preferably a 1 to 24 carbon atoms, more preferably a 1 to 12 heterocyclic group, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), Acyl group (preferably an acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, for example, an acetyl group, pivaloyl group, 2-ethylhexyl group, benzoyl group, cyclohexanoyl group), alkylsulfonyl group (Preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, isopropylsulfonyl group, cyclohexylsulfonyl group), and arylsulfonyl group (preferably Is an arylsulfonyl group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, for example, a phenylsulfonyl group or a naphthylsulfonyl group). In addition, when Ra is substitutable, the substituent may be further substituted, and when substituted with a plurality of substituents, those substituents may be the same or different.

X ³ and X ⁴ are preferably each independently an oxygen atom or a sulfur atom, and particularly preferably X ³ and X ⁴ are all oxygen atoms.

In general formula (I-3), Y <^1> and Y <^2> respectively independently represent NRb, a sulfur atom, or a carbon atom, and Rb is synonymous with Ra in said X < ³ >.

Y ¹ and Y ² are preferably each independently NRb (Rb is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and particularly preferably Y ¹ and Y ² are both NH.

In general formula (I-3), R <^8> and Y <^1> couple | bonded with each other, and together with R <^8> , Y <^1> , and a carbon atom, a 5-membered ring (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetra Hydrothiophene, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, 6-membered ring (e.g. cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylenesul A feed, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline) or a seven-membered ring (for example, cycloheptane, hexamethyleneimine) may be formed.

In general formula (I-3), R <^9> and Y <^2> may combine with each other, and may form the 5-, 6-, or 7-membered ring with R <^9> , Y <^2> , and a carbon atom. Examples of the 5-, 6-, or 7-membered ring to be formed include a ring in which one bond in the ring formed of R ⁸ and Y ¹ and a carbon atom is changed to a double bond.

In the general formula (I-3), when the 5-membered, 6-membered, and 7-membered ring formed by bonding of R ⁸ and Y ¹ and R ⁹ and Y ² is a ring which can be further substituted, any of the above substituents R It may be substituted by the group demonstrated in the above, and when substituted by two or more substituents, those substituents may be same or different.

In General Formula (I-3), X ⁵ represents a group which can be bonded to Ma. X ⁵ is, for example, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, an aliphatic imide (e.g., succinimide, maleimide, glutalimide, diacetamide, etc.). And succinic acid imide and maleimide are preferable. The monovalent group, aromatic imide group, or heterocyclic imide derived from (for example, phthalimide, naphthalimide, 4- Bromophthalimide, 4-methylphthalimide, 4-nitrophthalimide, naphthalene carboxyimide, tetrabromophthalimide, etc. are mentioned, Preferably phthalimide and 4-bromophthalimide are mentioned. Or a carboxylic acid derived from an aromatic carboxylic acid (for example, benzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, or 4-methylphthalimide). Chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxybenzoic acid, 4-t-butylbenzoic acid Etc., Preferably, monovalent group derived from benzoic acid, 4-methoxy benzoic acid, salicylic acid, etc., aliphatic carboxylic acid (for example, formic acid, acetic acid, acrylic acid, methacrylic acid, ethane) are mentioned. Acid, propanoic acid, lactic acid, pivalic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, 2-hexa Decyloctadecanoic acid, 2-hexyldecanoic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 5-norbornene-2-carboxylic acid, 1-adamantanecarboxylic acid, etc. are mentioned, Preferably, Is a monovalent group derived from acetic acid, methacrylic acid, lactic acid, pivalic acid, 2-ethylhexanoic acid, stearyl acid, and the like, dithiocarbamic acid (for example, dimethyldithiocarbamic acid, diethyl) Dithiocarbamic acid and dibenzyldithiocarbamic acid.) Monovalent group derived from a sulfonamide (for example, benzene) Phonamide, 4-chlorobenzene sulfonamide, 4-methoxybenzene sulfonamide, 4-beta benzene sulfonamide, 2-methylbenzene sulfonamide, methane sulfonamide is mentioned, Preferably benzene sulfonamide and methane sulfonamide Monovalent group derived from a monovalent group derived from a hydrohydric acid (for example, aceto hydroxamic acid, an octahydroxysamic acid, a benzohydric acid), a nitrogen-containing ring compound ( Hydantoin, 1-benzyl-5-ethoxyhydantoin, 1-allylhydantoin, 5,5-diphenylhydantoin, 5,5-dimethyl-2,4-oxazolidinedione, barbituric acid, imidazole , Pyrazole, 4,5-dicyanoimidazole, 4,5-dimethylimidazole, benzimidazole, 1H-imidazole-4,5-dicarboxylic acid diethyl, and the like. 1-benzyl-5-ethoxyhydantoin, 5,5-dimethyl-2,4-oxazolidinedione, 4,5-dicyanoimidazole, 1H-imidazole-4,5-dicarboxylic acid diethyl 1) derived from It represents a group.

Among them, X ^{5 is preferably a} halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic imide group, an aromatic imide group, a sulfonic acid group or a nitrogen-containing ring compound in terms of production, and a hydroxyl group, an aliphatic carboxylic acid group, and an aromatic compound. More preferred are imide groups and nitrogen-containing ring compounds. a represents 0, 1, or 2.

The preferable aspect of a compound represented by general formula (I-3) is shown below. That is, R ² to R ⁵ , R ⁷ , and Ma are each a preferred form of a complex containing a compound represented by the general formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are each independently NRa. (Ra is a hydrogen atom, an alkyl group, a heterocyclic group) or an oxygen atom, Y ¹ and Y ² are each independently NRb (Rb is a hydrogen atom or an alkyl group), a nitrogen atom, or a carbon atom, X ⁵ is an oxygen atom or R ⁸ and R ⁹ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R ⁸ and Y ¹ are bonded to each other to form a 5 or 6 membered ring. And R ⁹ and Y ² are bonded to each other to form a five-membered or six-membered ring. a is the form represented by 0 or 1.

The more preferable aspect of a compound represented by general formula (I-3) is shown below. That is, R ² to R ⁵ , R ⁷ and Ma are each a preferred form of a complex containing a compound represented by the general formula (I) and a metal atom or a metal compound, X ³ and X ⁴ are oxygen atoms, and Y ¹ is NH, Y ² is a nitrogen atom, X ⁵ is a group bonded through an oxygen atom or a nitrogen atom, and R ⁸ and R ⁹ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group Or R ⁸ and Y ¹ are bonded to each other to form a 5- or 6-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5- or 6-membered ring. a is the form represented by 0 or 1.

Hereinafter, the specific example of the dipyrromethene type metal complex compound which the compound represented by the said General formula (I) used for this invention arrange | positioned to a metal atom or a metal compound is shown. However, the present invention is not limited to these.

Exemplary compounds (1) to (39) are exemplary compounds of general formula (I-3) among the exemplary compounds of dipyrromethene-based metal complex compounds wherein compounds represented by these general formulas (I) are assigned to metal atoms or metal compounds It is also.

In addition to the above exemplary compounds, the exemplary compounds (Ia-3) to (Ia-83), (Ia-1) to (IIa-20), (I-1) to (I-36) described in Japanese Patent Laid-Open No. 2008-292970. ) (II-1) to (II-11), and (III-1) to (III-103), Exemplary Compounds (I-1) to (I-35) described in Japanese Patent No. 3324279, Japanese Patent No. Exemplary compounds (I-1) to (I-13) described in No. 3279035, Exemplary compounds (2-1) to (2-32) described in Japanese Patent Laid-Open No. 11-256057, (3-1) to (3- 32), (4-1) to (4-26), and (5-1) to (5-26), Exemplary Compounds (I-1) to (I-6) described in JP 2005-77953, And (VII-1) to (VII-8), Exemplary Compounds (1-1) to (1-45) described in Japanese Patent Laid-Open No. 11-352686, Exemplary Compounds of Japanese Patent Laid-Open 2000-19729 (1-1) ) To (1-50), and exemplary compounds (1-1) to (1-45) described in Japanese Patent Laid-Open No. 11-352685 are also assigned to a metal atom or a metal compound. An example of a dipyrromethene type metal complex compound is mentioned.

[Dispersion Composition]

The colored photosensitive composition of the present invention preferably includes a dispersion composition. The dispersion composition contained preferably as a method of obtaining the coloring photosensitive composition of this invention is demonstrated.

In the coloring photosensitive composition of this invention, 15 mass% or more of (B) specific dye is adsorb | sucking to the surface of (A) blue pigment. By setting the adsorption rate of the specific dye (B) to the surface of the (A) blue pigment to the said range, the colored layer obtained by the coloring photosensitive composition of this invention is favorable in heat resistance, and can exhibit high contrast. Although the method of adsorb | sucking a specific dye to a blue pigment may be sufficient, it is preferable to prepare the dispersion composition containing a blue pigment and a specific dye previously.

(Color material composition)

Moreover, in order to obtain this dispersion composition, it is preferable to premix a blue pigment and a specific dye to make a coloring material composition, and to carry out a dispersion process within the same system after that to make a dispersion composition. That is, it is preferable to prepare the slurry (color material composition) which mixed the pigment and dye, a solvent, a dispersing agent, an additive, an abrasive | polishing agent, etc. as needed, and to put this into a dispersion system collectively and to disperse | distribute. Therefore, in the present invention, before performing the salt milling described later, or before performing the dispersing treatment with the disperser, and when performing the multi-stage dispersing treatment in the disperser, the dyes are mixed before or after each step. When disperse | distributing a slurry, it is called premix. In addition, said "in the same system" means performing a dispersion process in the same dispersion apparatus and in the same dispersion batch.

Although various methods can be selected as a method of premixing, you may mix a blue pigment and a solid specific dye using the (F) organic solvent mentioned later, or melt | dissolve the specific dye in a blue pigment and the (F) organic solvent mentioned later You may mix dye solution.

As a method of mixing, a method using a conventional stirrer or the like may be used, and a two-stage roll, a three-stage roll, a ball mill, a trom mill, a disper, a kneader, a cornider, a homogenizer, a blender, a single screw, or a twin screw extruder may be used. May be kneaded while giving a strong shear force, but a kneading method is preferable from the viewpoint of increasing the adsorption rate of the dye.

(Salt milling)

Since the pigment is usually aggregated and disintegrated before dispersing, it is preferable that the salt milling treatment described below is performed as the pigment miniaturization treatment. At this time, it is also possible to prepare the said color material composition by adding a specific dye in solution or solid state at the time of salt milling as a mixing method of a dye and a pigment.

The miniaturization of the pigment is achieved by preparing a high viscosity liquid composition together with the pigment, the water-soluble organic solvent, and the water-soluble inorganic salts, and performing a process (salt milling) by adding a stress using a wet mill or the like. At this time, if necessary, a specific dye may be added together with the pigment in a solution or solid phase to obtain a colorant mixture.

As a water-soluble organic solvent used for the pigment refining process, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, di Ethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate and the like.

It is also possible to use other solvents having low water solubility or having no water solubility such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, But are not limited to, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, , Dimethyl sulfoxide, N-methyl pyrrolidone and the like may be used.

1 type of solvents used for the refinement | miniaturization process of a pigment may be sufficient, and may mix and use two or more types as needed.

Examples of the water-soluble inorganic salts used in the micronization step of the pigment include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.

The use amount of the water-soluble inorganic salt in the refinement | miniaturization process is 1-50 mass times of a pigment, and many have a grinding effect, but a more preferable quantity is 1-10 mass times from the point of productivity. Moreover, it is preferable to use the inorganic salt whose moisture is 1% or less.

The usage-amount of the water-soluble organic solvent in a refinement | miniaturization process is the range of 50 mass parts to 300 mass parts with respect to 100 mass parts of pigments, Preferably it is the range of 100 mass parts to 200 mass parts.

There are no particular restrictions on the operating conditions of the wet grinding device in the pigment miniaturization process. However, in order to effectively advance the grinding by the grinding media, the operating conditions when the device is the kneader are 10 to 200 rpm. It is preferable that the larger the rotation ratio of the two axes is, the larger the grinding effect is. The operating time is preferably from 1 hour to 8 hours together with the dry milling time, and the internal temperature of the apparatus is preferably from 50 to 150 占 폚. In addition, the water-soluble inorganic salt which is a grinding media has a grinding | pulverization particle size of 5-50 micrometers, and a distribution of particle diameter is sharp, and spherical shape is preferable.

The composition ratio of the blue pigment and the specific dye in the color material composition is preferably 1: 1 to 10: 1 in terms of mass, and more preferably 2: 1 to 10: 1. By setting it as this range, the adsorption rate of the specific dye to the surface of the blue pigment can be 15 mass% or more of a specific dye, and the effect of this invention can be exhibited.

Moreover, as for the sum total of the pigment and dye in a color material composition, 10 mass%-60 mass are preferable with respect to the total solid in a color material composition.

(Method for Producing Dispersion Composition)

A dispersion composition is obtained by disperse | distributing a blue pigment and a specific dye using the (F) organic solvent mentioned later. At this time, it is preferable to use the said color material composition instead of a blue pigment and a specific dye.

In addition, the dispersion composition mentioned later, a pigment derivative, and other components may be added, and pigments other than a blue pigment may be added.

The dispersion composition in this invention adds each component collectively or divides them, for example, glass of 0.01 mm-1 mm particle diameter using dispersers, such as a sand grinder of a vertical or horizontal type, a pin mill, a slit mill, It can be obtained by performing microdispersion treatment with beads made of zirconia or the like.

When disperse | distributing a blue pigment and a specific dye in advance, without passing through a color material composition, it is preferable to add dye in a dispersing apparatus during dispersion | distribution of a pigment, and it is especially preferable to add in the initial stage of dispersion. In this case, when a large amount of dye is added at a time, it tends to become a core, which is undesirable.

In addition, when adding a specific dye in a dispersing apparatus, you may add the dye solution of a specific dye, but it is preferable to add in solid state if possible from a viewpoint of solubility. Even when the dye solution is added, it is preferable that the dye concentration after the addition is as high as possible. This is because adsorption to the pigment is promoted as the dye concentration in the system of the dispersion composition is higher, and as a result, it is easier to achieve the heat resistance improvement which is the effect of the present invention. From this point of view, the addition of the dye is preferably performed at the time of salt milling or at the beginning of the dispersion. When using the multistage dispersion described later, the dye is preferably performed at the beginning of the first stage of dispersion.

As a method for preparing the dye solution, an organic solvent may be added to the dye and stirred, but a method of adding a powder dye into the stirred organic solvent is preferable in view of ease of dissolution. Although the whole amount of dye may be thrown in batches, it is also possible to divide | segment.

As the dissolution method of the dye, a solution containing the dye and the organic solvent described above may be agitated by a rod-shaped thing, a magnetic stirrer may be used, and a propeller-shaped agitator is usually rotated in a vessel at a constant speed and one direction. It may be melted with a stirrer. Moreover, you may melt | dissolve by applying a shearing force with a mixer, a resolver, etc. You may heat and melt as needed.

In addition, a strong shear force is applied by using a two-stage roll, a three-stage roll, a ball mill, a trom mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw, or a twin screw extruder before performing the dispersion by the beads. It is also possible to perform the kneading treatment while giving.

Details of kneading and dispersing are described in T. C. Patton, "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964), and the present invention can also be applied to the present invention.

In addition, in dispersion, the initial stage of dispersion disperse | distributes by setting solid content in a dispersion composition higher than the solid content of a final dispersion composition, and diluting it with components other than coloring components, such as an organic solvent and another high molecular compound, when it approaches the end of dispersion. The method is also a preferred form.

The preparation method of this dispersion composition is also a preferable form which disperse | distributes further by dividing into two stages or multiple stages of rough dispersion and fine dispersion typically.

In other words, when the concentration of the specific dye in the dispersion composition at the beginning of dispersion is Ci and the concentration of the specific dye in the dispersion composition after completion of the dispersion (the concentration of the specific dye after the concentration adjustment when the concentration is adjusted after completion of dispersion) is defined as Cf. It is preferable to disperse | distribute by following two or more steps to satisfy | fill Cf relationship.

When premixing is carried out, Ci is the concentration of the specific dye in the premixing. If premixing is not carried out, Ci is the concentration in the first stage of dispersion (coarse dispersion in two stages of dispersion). It is the concentration of a specific dye, and the concentration of a specific dye at the start of dispersion when dispersed in one stage without premixing. In addition, Cf is the density | concentration of the specific dye in the last stage of dispersion (precision dispersion in two stage dispersion | distribution), and in the case of adjusting concentration after dispersion, the density | concentration of the specific dye after concentration adjustment corresponds to said Cf.

In this way, the dye is more easily adsorbed to the pigment surface at high concentration, and the dye is adsorbed to the pigment surface gradually as the pigment disperses, and the dispersion proceeds while achieving the adsorption equilibrium, so that the adsorption rate can be increased. If Ci = Cf, even if the concentration is finally adjusted, since the dye concentration is already low from the time of introduction, it may take time to reach the adsorption equilibrium, and in some cases, the final adsorption rate may be lowered due to the inhibition of adsorption by a dispersant or an additive. This is not desirable because there is.

Moreover, according to this method, since the initial stage of dispersion has a large solid content, a high shear force is applied to a dispersion liquid, dispersion | distribution of a pigment easily advances by this shearing, and high dispersibility is obtained, and it is a preferable form.

Further, it is preferable to set Ci to be 1.1 to 10 times, more preferably 1.1 to 5 times, of Cf. Within this range, a dispersion composition having a high dispersibility can be easily obtained.

(Other components contained in the dispersion composition)

Hereinafter, dispersants and pigment derivatives which are preferably included in the dispersion composition of the present invention will be described.

(Dispersant)

As a dispersing agent, many kinds of compounds can be used specifically, For example, organosiloxane polymer KP341 [made by Shin-Etsu Kagaku Kogyo Co., Ltd.], (meth) acrylic-type (co) polymer polyflow No. 75, No. 90, No. Cationic surfactants such as 95 [manufactured by Kyoe Shisha Kagaku Kogyo Co., Ltd.] and W001 [manufactured by Yusho Corporation]; Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol distearate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (all manufactured by Chiba Specialty Chemical Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Polymer dispersants such as Disperse Aid 9100 (all manufactured by Sanofko Corp.); Various solvent dispersants (manufactured by Nihon Lubrizol Co., Ltd.) such as Solsper's 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) And Ionet S-20 (manufactured by Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by BYK-CHEMIE).

- Polymer dispersant -

The dispersion composition in the present invention preferably contains a polymer dispersant described below as a dispersant.

The dispersion composition in the present invention is a high molecular compound having at least one of the structural units represented by the following general formula (II) or the following general formula (III) and at least one of the structural units having an acid group (hereinafter, "specifically Polymer "may be referred to.

In said general formula (II) and general formula (III), R <^1> -R <^6> represents a hydrogen atom or monovalent organic group each independently, X <^1> and X <^2> respectively independently represent -CO-, -C (= O) ) O-, -CONH-, -OC (= O)-or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and A ¹ and A ² are each independently 1 An organic group is represented, m and n each independently represent an integer of 2 to 8, and p and q each independently represent an integer of 1 to 100.

(Structural Unit Represented by Formula (II) or Formula (III))

The structural unit represented by the said general formula (II) or (III) is contained as a repeating unit in a specific polymer.

In General Formula (II) and General Formula (III), each of R ¹ to R ⁶ independently represents a hydrogen atom or a monovalent organic group. As monovalent organic group, a substituted or unsubstituted alkyl group is preferable. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

When the alkyl group has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), methoxy group, ethoxy group and cyclohexyloxy group. Etc. can be mentioned.

Preferred examples of the alkyl group include alkyl groups such as methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n- A 2-hydroxypropyl group, and a 2-methoxyethyl group.

As R ¹ , R ² , R ⁴ , and R ^{5, a} hydrogen atom is preferable, and as R ³ and R ⁶ , a hydrogen atom or a methyl group is most preferable from the point of adsorption efficiency to the pigment surface.

X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. Especially, -C (= O) O-, -CONH-, and a phenylene group are preferable from a viewpoint of adsorption to a pigment, and -C (= O) O- is the most preferable.

L ¹ and L ² each independently represent a single bond or a divalent organic linking group. As a divalent organic coupling group, a substituted or unsubstituted alkylene group and the bivalent organic coupling group which consists of the partial structure containing the said alkylene group and hetero atom or hetero atom are preferable. Here, as an alkylene group, a C1-C12 alkylene group is preferable, A C1-C8 alkylene group is more preferable, A C1-C4 alkylene group is especially preferable. Moreover, as a hetero atom in the partial structure containing a hetero atom, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, An oxygen atom and a nitrogen atom are especially preferable.

Specific examples of preferred alkylene groups include methylene, ethylene, propylene, trimethylene and tetramethylene.

When an alkylene group has a substituent, a hydroxyl group etc. are mentioned as said substituent, for example.

The divalent organic linking group has a partial structure including a heteroatom or a heteroatom selected from -C (= O)-, -OC (= O)-, -NHC (= O)-at the terminal of the alkylene group, It is preferable from the point of adsorption to a pigment that it is connected with the adjacent oxygen atom through the said hetero atom or the partial structure containing a hetero atom.

A ¹ and A ² each independently represent a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable.

Examples of preferred alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups. , Nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, Neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group is mentioned.

As a substituent of the substituted alkyl group, a group of monovalent nonmetallic atom groups except hydrogen is used, and a preferable example is a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, or an alkyl group. Thio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-aryl Amino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N -Alkyl-N-arylcarbamoyloxy group, alkyl sulfoxy group, aryl sulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylurea Pottery, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido Group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group , N ', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkyl Ureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulphi Neyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO ₃ H) and its conjugated base group (hereinafter referred to as sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group , N-alkyl sulfinamoyl group, N, N-dialkyl sulfinamoyl group, N-aryl sulfinamoyl group, N, N- diaryl sulfinamoyl group, N-alkyl-N-aryl sulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (-PO ₃ H ₂ ) and its conjugated base group (hereinafter referred to as phosphonato group), dialkylphosphono group (-PO ₃ (alkyl) ₂ ), diarylphosphono group (-PO ₃ (aryl) ₂ ), alkyl Aryl phosphono group (-PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonato group), monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated salts device (hereinafter, aryl phosphine Estepona earthenware And is referred to), phosphono oxy group (-OPO ₃ H ₂₎ and its conjugated salts device (hereinafter, referred to as phosphonate NATO group), dialkyl phosphono oxy group _{(-OPO 3 (alkyl) 2)} , diaryl Phosphonooxy group (-OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (-OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (-OPO ₃ H (alkyl)) and its conjugate salt unit (hereinafter, referred to as the NATO phosphonic group), monoaryl phosphono oxy group (-OPO ₃ H (aryl)) and its conjugated salts device (hereinafter referred to as after, Nato aryl phosphonate group), a cyano group , Nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, silyl group.

Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.

Examples of the substituent include an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N, N-dialkylamino group, an N, N-diarylamino group, An aryl group, an alkenyl group, an alkynyl group and a silyl group are preferable from the viewpoint of dispersion stability.

Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, Phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonyl A phenyl group, N-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, a sulfo phenyl group, a sulfonatophenyl group, a phosphonophenyl group, a phosphonatophenyl group, etc. are mentioned.

As A <^1> and A <^2> , the C1-C20 linear form, the C3-C20 branched form, and the C5-C20 cyclic alkyl group are preferable from dispersion stability and developability, and it is 4-15 carbon atoms. More preferably, the linear, branched, alkyl group having 4 to 15 carbon atoms, and the cyclic alkyl group having 6 to 10 carbon atoms are more preferable, and the linear alkyl group having 6 to 10 carbon atoms and branched alkyl group having 6 to 12 carbon atoms are more preferable. .

m and n each independently represent an integer of 2 to 8; From the viewpoint of dispersion stability and developability, m and n are preferably 4 to 6, and most preferably 5.

p and q respectively independently represent the integer of 1-100. Two or more of p and q may be different. From the viewpoints of dispersion stability and developability, p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20.

The specific polymer in this invention contains at least 1 sort (s) of the structural unit represented by the said general formula (II), or at least 1 sort (s) of the structural unit represented by the said general formula (III), or the said general formula (II) At least 1 sort (s) of the structural unit represented by the following, and at least 1 sort (s) of the structural unit represented by the said General formula (III) is included. Here, in the said general formula (II) and general formula (III), the following combination is especially preferable form. That is, R ¹ , R ² , R ⁴ , and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are preferably hydrogen atoms or methyl groups. X ¹ and X ² are preferably -C (= O) O-. L ¹ and L ² include a heteroatom or a heteroatom selected from -C (= 0)-, -OC (= 0)-, and -NHC (= 0)-at the terminal of the alkylene group having 1 to 4 carbon atoms; Preferred are divalent organic linking groups having a partial structure and connected to adjacent oxygen atoms via said heteroatoms or substructures comprising heteroatoms. m and n are preferably 5, and p and q are preferably 5 to 20.

As a specific polymer in this invention, it is preferable to contain at least 1 sort (s) of the structural unit represented by said general formula (II) from the point of dispersion stability.

Moreover, as a structural unit represented by the said General formula (II), it is more preferable that it is a structural unit represented with the following general formula (II) -2.

In said general formula (II) -2, R <^1> -R <^3> represents a hydrogen atom or monovalent organic group each independently, La represents a C2-C10 alkylene group, Lb is -C (= O)-or -NHC (= O)-, A <^1> represents monovalent organic group, m represents the integer of 2-8, p represents the integer of 1-100.

The monovalent organic group represented by R <^1> -R <^3> , A <^1> , and the detail and preferable aspect of m and p are the same as the case in the said General formula (II).

La is more preferably an alkylene group having 2 to 8 carbon atoms, and still more preferably an alkylene group having 2 to 4 carbon atoms. Specific examples thereof include an ethylene group, a propylene group, a trimethylene group and a tetramethylene group. When an alkylene group has a substituent, a hydroxyl group etc. are mentioned as said substituent, for example.

The structural unit represented by the general formula (II), (III) or (II) -2 is a polymer by polymerizing or copolymerizing a monomer represented by the following general formula (i), (ii) or (i) -2, respectively. It is introduced as a repeating unit of the compound.

In General Formulas (i), (ii) and (i) -2, R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent -CO-,- C (= O) O-, -CONH-, -OC (= O)-or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and La has 2 to 10 carbon atoms Represents an alkylene group, Lb represents -C (= 0)-or -NHC (= 0)-, A ¹ and A ² each independently represent a monovalent organic group, and m and n are each independently 2 to The integer of 8 is shown, p and q respectively independently represent the integer of 1-100.

R ¹ to R ⁶ , X ¹ and X ² , L ¹ and L ² , A ¹ and A ² , m and n, p and q agree with the above general formulas (II), (III) and (II) to be.

Hereinafter, although the preferable specific example [monomer (A-1)-(A-24)] of the monomer represented by general formula (i), (ii) or (i) -2 is given, this invention is limited to these no.

The specific polymer in this invention contains at least 1 sort (s) of the structural unit represented by the said General formula (II) or (III), may contain only 1 type, and may contain 2 or more types.

The content of the structural unit represented by the general formula (II) or the general formula (III) in the specific polymer is not particularly limited, but the dispersibility of the pigment when the total structural unit contained in the polymer is 100% by mass. And from the viewpoint of making developability compatible, it is preferable to contain 5 mass% or more of said structural units, It is more preferable to contain 30 mass% or more, It is more preferable to contain 40 mass%-60 mass%.

(Structural unit having an acid group)

The specific polymer in this invention contains the structural unit (acidic group containing structural unit) which has an acidic radical. The acid groups of the acid group-containing structural units act as adsorbers for the pigments or pigment derivatives.

As an acidic radical in the acidic radical containing structural unit in this invention, the acidic radical of pKa10 or less is preferable. As a specific example of the acid group of pKa10 or less, a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, a phenol group etc. are mentioned, for example. Among these, a carboxylic acid group is used most suitably from a viewpoint which compatible pigment dispersibility and developability.

In the acidic radical-containing structural unit in the present invention, the acidic radical may be directly bonded to the main chain of the specific polymer or may be bonded to the main chain of the specific polymer via the linking chain.

The linking chain connecting the main chain and the acid group of the specific polymer is preferably a linking group containing a functional group selected from an aromatic ring, an ether group, an ester group, an amide group, urea group and / or a urethane group. Since the functional group itself exhibits adsorptivity to the pigment, it is considered that when the functional group is in a position close to the acid group in the acid group-containing structural unit, there is an effect of increasing the adsorption to the pigment or the pigment derivative.

Here, the main chain of a specific polymer refers to a site connected by polymerization when a polymer is synthesized. For example, in the case of a polymer obtained by polymerizing methacrylic acid ester, the methacrylic site refers to an alkylene moiety linked by polymerization.

Also, the connector may be used by combining a plurality of connectors. For example, the aromatic ring and the ether group, the aromatic ring and the ester group, the aromatic ring and the urea group, the ether group and the urea group, the aromatic ring and the ether group and the urea group can be used in combination.

When the dispersion composition of the present invention comprises titanium black as a pigment, since titanium black has a nitrogen atom, a hydrogen bondable functional group is preferably used as the linking group of a specific polymer, and specifically, an amide group, a urea group, and a urethane group are preferable. Used.

Moreover, as a coupling group used for the acidic radical containing structural unit in this invention, it is preferable to introduce an aromatic ring. When the linking chain has an aromatic ring, entanglement of the polymer can be reduced by steric hindrance as compared with a normal alkyl chain and the like, and the dispersibility of the pigment can be improved since the aromatic ring is easily directed out of the polymer from the main chain portion.

Here, the aromatic ring represents a structure in which atoms having π electrons are cyclically arranged, and a ring which does not contain heteroatoms such as benzene ring, naphthalene ring, anthracene ring, pyridine ring, pyrrole ring, furan ring, carbazole ring And a ring containing a hetero atom such as a thiophene ring. Among them, a benzene ring, a naphthalene ring and a pyridine ring having high versatility can be suitably used, the benzene ring can be used more suitably, and it is more preferable that the structure is represented by the following formula (2).

In the formula (2), Y represents a linkage group with the main chain of the specific polymer, and S represents an acidic functional group. R has a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a heteroaryloxy group which may have a substituent, and a substituent The alkyloxycarbonyl group which may have, the aryloxycarbonyl group which may have a substituent, the alkylamide group which may have a substituent, the arylamide group which may have a substituent, a halogen group, and a nitro group are shown. N represents an integer of 0 to 4, and m represents an integer of 1 to 5.

In the formula (2), Y represents a linkage group with the main chain of the specific polymer. Although there is no limitation in particular as a structure of a coupling group, From the viewpoint of lowering pKa of an acidic group, it is preferable that the benzene ring and the main chain are connected by the electron withdrawing group, and it is more preferable that it is connected by ester group, an amide group, sulfonamide group, etc. It is more preferable that it is connected with ester group.

Specific preferred examples of Y are shown below, but Y is not limited to these structures. X represents a site bonding with a main chain of a specific polymer, and Z represents a site bonding with a benzene ring.

In said formula (2), R is a hydrogen atom, the alkyl group which may have a substituent, the aryl group which may have a substituent, the alkoxy group which may have a substituent, the aryloxy group which may have a substituent, and hetero which may have a substituent The aryloxy group, the alkyloxycarbonyl group which may have a substituent, the aryloxycarbonyl group which may have a substituent, the alkylamide group which may have a substituent, the arylamide group which may have a substituent, a halogen group, and a nitro group are shown. It is preferable that it is substituted by a hydrogen atom or an electron withdrawing group from the viewpoint of lowering the pKa of an acidic group, and the alkyloxycarbonyl group which may have a hydrogen atom and a substituent, the aryloxycarbonyl group which may have a substituent, and the alkylamide group which may have a substituent And an arylamide group which may have a substituent, a halogen group, a nitro group and a carboxyl group are preferable, and an alkyloxycarbonyl group which may have a hydrogen atom and a substituent, and the aryloxycarbonyl group which may have a substituent are more preferable.

The acid group-containing structural unit in the present invention is preferably a structural unit having a carboxylic acid group as the acid group (hereinafter may be referred to as a "carboxylic acid group-containing structural unit"). More preferably, it is a structural unit which has a carboxylic acid group couple | bonded with the main chain of a specific polymer through the linking chain which consists of atom groups which have four or more atoms except hydrogen atoms.

In the carboxylic acid group-containing structural unit, the carboxylic acid group is bonded to the main chain through the linking chain, whereby the flexibility of the carboxylic acid group moiety becomes high, and it becomes possible to interact with the pigment or the pigment derivative more efficiently. Moreover, since a carboxylic acid group also acts as a developable group, developability also improves by high flexibility. In this regard, the longer the linking chain is, the better.

On the other hand, when the linking chain is too long, the number of carboxylic acid group-containing structural units that can be introduced into the polymer decreases, and therefore, the number of carboxylic acid groups that can be introduced into the polymer decreases.

For the above reason, in the carboxylic acid group-containing structural unit, it is preferable that the linking chain connecting the main chain and the carboxylic acid group is composed of atomic groups having 4 to 100 atoms excluding hydrogen atoms, more preferably hydrogen atoms It consists of atomic groups having 6-60 atoms except for, More preferably, it consists of atomic groups having 8-20 atoms except hydrogen atoms.

In the said carboxylic acid group containing structural unit, the preferable form of the connection chain which connects the main chain and carboxylic acid group of a specific polymer is the same as the connection chain in the above-mentioned acidic radical containing structural unit, and combines several type of coupling group as a connection chain, The same can be used.

As a coupling group used for the said carboxylic acid group containing structural unit, it is preferable to introduce an aromatic ring like the acidic radical containing structural unit mentioned above, and its preferable aspect is also the same.

As a partial structure of the said carboxylic acid group containing structural unit, it is more preferable that it is a structure represented by following formula (1).

In the formula (1), Y, R, and n are synonymous with the formula (2). The carboxylic acid group may be introduced from a benzene ring through a linking group.

Although the specific example of the partial structure represented by said Formula (1) is shown below, the said partial structure is not limited to these specific examples. X represents a binding site with a main chain.

In the carboxylic acid group-containing structural unit, the linking chain preferably has an aromatic ring and is composed of atomic groups having 6 or more and 60 or less atoms except hydrogen atoms. More preferably, the aromatic ring is a benzene ring, and is a linking chain bonded to the main chain via the benzene ring or by an ester bond.

In the specific polymer in the present invention, the content of the carboxylic acid group-containing structural unit is preferably 50 mgKOH / g or more as an acid value in that the content of the precipitate in the developer when forming a colored region is suppressed. In order to effectively suppress the production of secondary aggregates, which are aggregates of pigment primary particles, or to effectively weaken the cohesion force of secondary aggregates, the content of the carboxylic acid group-containing structural unit is preferably 50 mgKOH / g to 200 mgKOH / g as an acid value. Do.

(Other structural units)

It is preferable that the specific polymer in this invention is a high molecular compound which further copolymerized the monomer which has a functional group which can adsorb | suck to a pigment in order to improve the adsorption property to a pigment.

As a monomer which has a functional group which can adsorb | suck to a pigment other than an acidic group, the monomer which has an organic pigment | dye structure or a heterocyclic structure, the monomer which has a basic nitrogen atom, the monomer which has an ionic group, etc. are mentioned specifically ,. Especially, the monomer which has an organic pigment | dye structure or a heterocyclic structure is preferable at the point of the adsorption power to a pigment.

The monomer (monomer) which has a functional group which can adsorb | suck to a pigment can be suitably selected according to the kind of pigment to be disperse | distributed, These may be used independently and may use 2 or more types together.

The specific polymer in this invention may further contain the structural unit derived from the vinyl monomer which can be copolymerized in the range which does not impair the effect.

Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, ( Meta) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. As specific examples of such vinyl monomers, there may be mentioned, for example, the following compounds. In addition, when showing one or both of "acryl and methacryl" in this specification, it may describe as "(meth) acryl."

Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate and isobutyl (meth) acrylate. T-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ( 2-ethoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 3-phenoxy-2-hydroxypropyl methacrylate, benzyl (meth) acrylate, (meth) acrylic acid Diethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth ) Triethylene glycol monomethyl ether (acrylate), triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, β-phenoxyethoxy (meth) acrylate Ethyl, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, Perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate, and the like.

As an example of maleic acid diester, dimethyl maleate, diethyl maleate, dibutyl maleate, etc. are mentioned.

Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate, and the like.

Examples of the itaconic acid diesters include dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, and the like.

As (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth ) Acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloyl morpholine, diacetone acrylamide, etc. are mentioned. Can be.

As an example of vinyl ether, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy ethyl vinyl ether, etc. are mentioned.

Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene and bromo Styrene, chloromethylstyrene, hydroxystyrene protected by a group which can be deprotected by an acidic substance (for example, t-Boc etc.), methyl vinyl benzoate, alpha-methylstyrene, etc. are mentioned.

Specific examples of the specific polymer in the present invention include the following exemplary compounds 1 to 35.

The preferred molecular weight of the specific polymer in the present invention is a weight average molecular weight (Mw) in the range of 5,000 to 100,000 and a number average molecular weight (Mn) in the range of 2,500 to 50,000. More preferably in the range of 10,000 to 50,000 in terms of weight average molecular weight (Mw) and in the range of 5000 to 30,000 in number average molecular weight (Mn). In particular, it is most preferred that the weight average molecular weight (Mw) is in the range of 20,000 to 400,000 and the number average molecular weight (Mn) is in the range of 5,000 to 20,000.

That is, the weight average molecular weight (Mw) of the specific polymer is preferably 1,000 or more from the viewpoint of effectively solving the secondary aggregates of aggregates of the primary particles of the pigment or effectively weakening the re-aggregation. From the viewpoint of developability when the color filter is produced by the colored photosensitive composition containing the dispersion composition, the weight average molecular weight (Mw) of the specific polymer is preferably 50,000 or less.

The specific polymer in the present invention can be produced by a conventional radical polymerization method.

Generally, suspension polymerization or solution polymerization is used. As a solvent used when synthesizing such a specific polymer, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2 -Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, Methyl lactate, ethyl lactate, etc. are mentioned. These solvents may be used singly or in combination of two or more. In addition, a radical polymerization initiator can be used at the time of radical polymerization, and a chain transfer agent (for example, 2-mercaptoethanol and dodecyl mercaptan) can be used further.

The content of the dispersant in the dispersion composition is preferably in the range of pigment: specific polymer (mass ratio) = 1: 0.1-1: 2, more preferably in the range of 1: 0.2-1: 1, still more preferably 1 It is in the range of 0.4 to 1: 0.7.

In addition, the dispersion composition may contain a pigment derivative.

A pigment derivative is a compound which introduce | transduced the acidic group, basic group, and aromatic group as a substituent into the side chain of organic pigment, and is different from a specific dye.

In the present invention, the blue pigment adsorbs a specific dye to the surface thereof, but a pigment derivative having a site having affinity with the specific polymer (polymer dispersant) is adsorbed onto the surface of the pigment to which the specific dye is not adsorbed. By using it as an adsorption point of a specific polymer, a pigment can be made into finer particle | grains and can be disperse | distributed in a coloring composition. In addition, the re-agglomeration can be prevented. That is, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant such as the specific polymer in the present invention by modifying the pigment surface on which the specific dye is not adsorbed.

Since the specific polymer in this invention has an acidic radical, the dispersibility of a pigment can be improved further and a fine pigment can be disperse | distributed further by using the basic pigment derivative which has a basic group as a pigment derivative. And by using the coloring photosensitive composition containing a basic pigment derivative, the color filter which is small in color concentration variation and excellent in color characteristics can be formed.

A pigment derivative is a compound which has an organic pigment as a mother skeleton and introduce | transduced an acidic group, a basic group, and an aromatic group into a side chain as a substituent. The organic pigment which becomes a mother skeleton specifically, a quinacridone pigment, a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoindolin type pigment, an iso indolinone pigment, a quinoline pigment, a diketopyrrolopyrrole pigment And benzoimidazolone pigments. The parent skeleton also includes light yellow aromatic polycyclic compounds such as naphthalene, anthraquinone, triazine and quinoline, which are not generally called pigments.

Examples of the pigment derivative include those disclosed in JP-A Nos. 11-49974, 11-189732, 10-245501, 2006-265528, 8-295810, and 11-199796 Those described in JP-A-2005-234478, JP-A-2003-240938, and JP-A-2001-356210 can be used.

When the pigment derivative is used in the dispersion composition of the present invention, the amount thereof is preferably in the range of 1% by mass to 80% by mass relative to the pigment, more preferably in the range of 3% by mass to 65% by mass , And particularly preferably from 5% by mass to 50% by mass. When the content is within this range, the pigment can be dispersed well while the viscosity is kept low, and dispersion stability after dispersion can be improved. And by apply | coating this coloring photosensitive composition to manufacture of a color filter, the transmittance | permeability is high, it has the outstanding color characteristic, and the high contrast color filter can be obtained.

In addition, in the range which does not impair the effect of this invention, you may use another high molecular compound simultaneously other than the specific polymer in this invention as needed. As other high molecular compounds, natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like are used.

Examples of the natural resin include rosin, and the modified natural resins include rosin derivatives, fibrin derivatives, rubber derivatives, protein derivatives, and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of the synthetic resin modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.

Examples of the synthetic resin include polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, polyurethanes, polyesters, poly (meth) acrylates, (meth) acrylic copolymers and naphthalenesulfonic acid formalin condensates. .

As content of the blue pigment in a dispersion composition, 20-70 mass% is preferable with respect to the total solid (mass) of a dispersion composition, and 30-60 mass% is more preferable. When content of a blue pigment is in the said range, color density is enough and it is effective also to ensure the outstanding color characteristic.

The content of the specific dye in the dispersion composition is preferably 5 to 40 mass%, more preferably 10 to 30 mass%, based on the total solid content (mass) of the dispersion composition. When the content of the specific dye is in the above range, the dispersion stability of the dispersion composition is good, and the color concentration is sufficient, which is effective for securing excellent color characteristics.

Moreover, it is preferable that it is 1-50 mass% with respect to the total solid of the said composition, and, as for content of the blue pigment in the coloring photosensitive composition of this invention, 1-30 mass% is more preferable.

Moreover, it is preferable that it is 0.1-25 mass% with respect to the total solid of the said composition, and, as for content of the specific dye in the coloring photosensitive composition of this invention, 0.1-15 mass% is more preferable. When content of a pigment and a specific dye exists in the said range, the colored layer obtained using the coloring photosensitive composition will have high brightness and high contrast, and it will become easy to satisfy the various characteristics calculated | required by coloring photosensitive compositions, such as developability.

[(C) Polymerizable compound]

The colored photosensitive composition of the present invention comprises at least one (C) polymerizable compound.

As the polymerizable compound, for example, it is a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected and used from components constituting a known composition, and paragraph number of Japanese Patent Laid-Open No. 2006-23696. And components described in paragraphs [0027] to [0053] of JP-A-2006-64921.

Moreover, the urethane addition polymeric compound manufactured using addition reaction of an isocyanate and hydroxyl group is also suitable, Unexamined-Japanese-Patent No. 51-37193, Unexamined-Japanese-Patent No. 2-32293, Unexamined-Japanese-Patent No. 2-16765 Urethane acrylates as described in Japanese Patent Application Laid-Open No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 Also suitable are urethane compounds having an ethylene oxide skeleton as described in this publication.

As other examples, polyester acrylates and epoxy resins as described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with (meth) acrylic acid. In addition, Japan Adhesion Association vol. 20, No. 7, pages 300 to 308 (1984), which are incorporated herein by reference, as photo-curable monomers and oligomers.

Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tri ((meth) acryloyloxy Ethyl) isocyanurate, pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, and the like are NK ester A-TMMT, NK ester A-TMM-3 , NK oligo UA-32P, NK oligo UA-7200 (above, Shinnakamura Kagaku Kogyo Co., Ltd. product), aronix M-305, aronix M-306, aronix M-309, aronix M-450, Aronix M-402, TO-1382, TO-2349 (above, Toagosei Co., Ltd. make), V # 802 [Osaka Yuki Kagaku Kogyo Co., Ltd. make] are mentioned as a preferable example.

Also, the compounds described in paragraphs [0031] to [0061] of JP-A No. 2009-265630 are also preferable, and among them, the following compounds described in [0055] to [0059] are preferable.

These polymeric compounds can be used individually or in combination of 2 or more types.

As content (in the case of 2 or more types, total content) of the polymeric compound in the total solid in a coloring photosensitive composition, 10 mass%-80 mass% are preferable, 15 mass%-75 mass% are more preferable, 20 mass% 60 mass% is especially preferable.

[(D) Photopolymerization Initiator]

The colored photosensitive composition of the present invention preferably contains at least one photopolymerization initiator.

There is no restriction | limiting in particular if a photoinitiator can superpose | polymerize the said polymeric compound, It is preferable to select from a viewpoint of a characteristic, start efficiency, absorption wavelength, availability, cost, etc.

A photoinitiator is a compound which is exposed by exposure light, and initiates and accelerates superposition | polymerization of a polymeric compound. The compound which responds to actinic light of wavelength 300nm or more and starts and accelerates superposition | polymerization of a polymeric compound is preferable. In addition, a photopolymerization initiator which does not directly react with an actinic ray having a wavelength of 300 nm or more can be preferably used in combination with a sensitizer.

Specific examples thereof include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, An oxime compound, an acylphosphine oxide, a benzophenone compound, an acetophenone compound and a derivative thereof, and the like can be given.

Of these, oxime ester compounds and hexaarylbimidazole compounds are preferable from the viewpoint of sensitivity.

As an oxime ester compound, Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2001-233842, Unexamined-Japanese-Patent No. 2004-534797, International Publication 2005/080337, International Publication 2006/018973, Japan The compounds described in Japanese Patent Application Laid-Open No. 2007-210991, Japanese Patent Laid-Open No. 2007-231000, Japanese Patent Laid-Open No. 2007-269779, Japanese Patent Laid-Open No. 2009-191061, and International Publication No. 2009/131189 can be used. .

As a specific example, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione and 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl ] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime ) -1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Ethanone, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1 -[9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl ) -9H- Le carbazole-3-yl] ethanone, and the like. However, the present invention is not limited thereto.

Moreover, in this invention, the compound represented by the following general formula (A) is also suitable as an oxime ester compound which is a photoinitiator from a viewpoint of the coloring in a sensitivity, time-lapse stability, and heat resistance.

In Formula (A), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ represents —R, —OR, —COR, —SR, —CONRR ′, Or -CN, and R ² and R ³ each independently represent -R, -OR, -COR, -SR, or -NRR '. R and R 'each independently represent an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group, and the alkyl group and the aralkyl group One or more of the carbon atoms constituting the alkyl chain may be substituted with an unsaturated bond, an ether bond, or an ester bond, and R and R 'may be bonded to each other to form a ring.

In general formula (A), when X <^1> , X <^2> and X <^3> represent a halogen atom, fluorine, chlorine, bromine, and iodine are mentioned, X <^1> , X <^2> and X <^3> represent an alkyl group. Examples of the alkyl group in the case of being represented are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, amyl, isoamyl, third amyl, hexyl, heptyl, octyl, isooctyl, 2 Ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, eth Methoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzooxazole-2'- And 1) ethenyl.

Especially, it is preferable that all of X <^1> , X <^2> and X <^3> represent a hydrogen atom, or X <^1> represents an alkyl group, and all of X <^2> and X <^3> represent a hydrogen atom.

Examples of the alkyl group represented by R and R 'in the general formula (A) include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, Butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, n-propyl, isopropyl, n-butyl, isobutyl, Propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, perfluoroethyl, perfluoroethyl , 2- (benzoxazol-2'-yl) ethenyl, and the like.

Examples of the aryl group represented by R and R 'include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like.

Examples of the aralkyl group represented by R and R 'include benzyl, chlorobenzyl,? -Methylbenzyl,?,? - dimethylbenzyl, phenylethyl, phenylethenyl and the like.

Examples of the heterocyclic group represented by R and R 'include pyridyl, pyrimidyl, furyl, thiophenyl and the like.

Examples of the ring formed by bonding R and R 'to each other include a piperidine ring and a morpholine ring.

As R <^2> and R <^3> comprised including said R and R ', a methyl group, a hexyl group, a cyclohexyl group, -S-Ph, -S-Ph-Cl, and -S-Ph-Br are respectively especially preferable. Form.

X ¹ , X ² , and X ^{3 in the} general formula (A) are also hydrogen atoms in the photopolymerization initiator; R ¹ is an alkyl group, especially a methyl group; R ² is an alkyl group, especially a methyl group; It is especially suitable as a photoinitiator that R <^3> is an alkyl group, especially an ethyl group.

Therefore, preferred specific examples of the photopolymerization initiator represented by the above-mentioned general formula (A) include the compounds A to F exemplified below. However, the present invention is not limited by the following compounds.

The photopolymerization initiator represented by the general formula (A) can be synthesized, for example, by the method described in JP-A-2005-220097.

The compound represented by general formula (A) used for this invention has an absorption wavelength in the wavelength range of 250 nm-500 nm. More preferably, what has an absorption wavelength in the wavelength range of 300 nm-380 nm is mentioned. Particularly, it is preferable that the absorbance at 308 nm and 355 nm is high.

Moreover, in this invention, the compound represented by following General formula (B) is also suitable as an oxime ester compound which is a photoinitiator from a viewpoint of a sensitivity, time-lapse stability, and coloring at the time of post-heating.

In the general formula (B), R ²² represents a monovalent substituent. A ²² represents a divalent linking group, and Ar represents an aryl group. n is an integer of 0 to 5; X <^22> represents a monovalent substituent and when n is an integer of 2-4, two or more X <^22> may be same or different.

The monovalent substituent represented by R ²² is preferably a monovalent non-metallic atom shown below.

Examples of the monovalent nonmetal atomic group represented by R ²² include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, , A heterocyclic group which may have a substituent, and the like.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group cyclopentyl group, a cyclohexyl group and a trifluoromethyl group.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group and a 2-naphthyl group.

The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group and an ethylsulfonyl group.

The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group.

As an acyl group which may have a substituent, a C2-C20 acyl group is preferable, For example, an acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl group, 2 -Naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2- Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-sia A nobenzoyl group, 4-methoxy benzoyl group, etc. are mentioned.

As the heterocyclic group which may have a substituent, an aromatic or aliphatic heterocycle including a nitrogen atom, an oxygen atom, a sulfur atom, and a person atom is preferable. For example, a thienyl group, a furyl group, and a pyranyl group.

As said R <^22> , the acyl group which has an unsubstituted or substituted group from a point of high sensitivity is more preferable, and the acetyl group, propionyl group, benzoyl group, and toluyl group which have an unsubstituted or substituent specifically, are preferable.

As said substituent, group represented by the following structural formula is mentioned, for example, Especially, any of (d-1), (d-4), and (d-5) is preferable.

Examples of the divalent linking group represented by A ²² include alkylene having 1 to 12 carbon atoms, which may have a substituent, cyclohexylene which may have a substituent, and alkynylene which may have a substituent.

As a substituent which can be introduce | transduced into these groups, For example, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an alkoxy group, such as a methoxy group, an ethoxy group, and a tert-butoxy group, a phenoxy group, p-tolyl jade Alkoxycarbonyl groups, such as an aryloxy group, methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group, such as a time period, etc. are mentioned.

Especially, as said A <^22> , the alkylene group substituted by the unsubstituted alkylene group and alkyl group (for example, methyl group, ethyl group, tert- butyl group, and dodecyl group) from the point which raises a sensitivity and suppresses coloring by the elapse of a heating time. Alkylene groups substituted with alkenyl groups (e.g., vinyl and allyl groups), aryl groups (e.g., phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, Preference is given to alkylene groups substituted with styryl group).

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.

Specifically, Ar is a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, etc. are mentioned. Especially, a substituted or unsubstituted phenyl group is preferable at the point which raises a sensitivity and suppresses coloring by the passage of a heating time.

When the phenyl group has a substituent, examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy group such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p. -Acyloxy groups such as aryloxy groups such as tolyloxy group, methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group, acetyl group, benzoyl group, Dialkyl, such as acyl groups, such as an isobutyryl group, acryloyl group, a methacryloyl group, and methoxylyl group, alkylamino groups, such as a methylamino group and a cyclohexylamino group, a dimethylamino group, a diethylamino group, a morpholino group, and a piperidino group And alkyl groups such as amino groups, phenylamino groups, methyl groups, ethyl groups, tert-butyl groups and dodecyl groups, hydroxy groups and carboxyl groups.

In the general formula (B), the structure of &quot; SAr &quot; formed from S adjacent to Ar is preferable from the viewpoint of sensitivity as long as it has the structure shown below.

Examples of the monovalent substituent represented by X ²² include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent The aryloxy group which may have, the alkylthiooxy group which may have a substituent, the arylthiooxy group which may have a substituent, a halogen atom, etc. are mentioned.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, An imidazolyl group, an imidazolyl group, a phenanthryl group and the like.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a terphenyl group, a quaterphenyl group, o-, -Tolyl group, xylyl group, and the like.

As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, For example, a vinyl group, an allyl group, a styryl group, etc. are mentioned.

As an alkynyl group which may have a substituent, a C2-C10 alkynyl group is preferable, for example, an ethynyl group, a propynyl group, a propargyl group, etc. are mentioned.

The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group and benzyloxy group.

The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, and examples thereof include a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, A 2-methoxyphenyloxy group, and the like.

The alkylthioxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms, and examples thereof include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, A tert-butylthioxy group, a pentylthioxy group, an isopentylthioxy group, a hexylthioxy group, a heptylthioxy group, an octylthioxy group, a 2-ethylhexyl A thiooxy group, a decylthioxy group, a dodecylthioxy group, an octadecylthioxy group, a benzylthioxy group and the like.

The arylthioxy group which may have a substituent is preferably an arylthioxy group having 6 to 30 carbon atoms, and examples thereof include a phenylthioxy group, a 1-naphthylthioxy group, a 2-naphthylthioxy group, A 2-methoxyphenylthioxy group, a 2-methoxyphenylthioxy group, a 3-chlorophenylthioxy group, a 3-trifluoromethylphenylthioxy group, a 3-cyano A 4-fluorophenylthioxy group, a 4-methoxyphenylthioxy group, a 4-dimethylaminophenylthioxy group, a 3-nitrophenylthioxy group, 4-methylsulfanylphenylthioxy group, 4-phenylsulfanylphenylthioxy group, and the like.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

Examples of the halogenated alkyl group which may have a substituent include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group, and a tribromomethyl group.

Examples of the amide group which may have a substituent on the N-phase include an N, N-dimethyl amide group and an N, N-diethyl amide group.

Among these, X ²² is an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent from the point of solvent solubility and the improvement of absorption efficiency of a long wavelength region. An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, an arylthiooxy group which may have a substituent, a halogenated alkyl group which may have a substituent, an amino group which may have a substituent Or the amide group which may have a substituent in the N position is preferable, and the alkyl group which may have a substituent is especially preferable.

In the general formula (B), n represents an integer of 0 to 5, but from the viewpoint of ease of synthesis, an integer of 0 to 3 is preferable, and an integer of 0 to 2 is more preferable.

When there are plural X ²² in the formula (B) are a plurality of X ²² it may be different gatahdo.

Specific examples of the oxime photopolymerization initiator represented by the above general formula (B) are shown below.

The compound represented by general formula (B) used for this invention has an absorption wavelength in the wavelength range of 250 nm-500 nm. More preferably, what has an absorption wavelength in the wavelength range of 300 nm-380 nm is mentioned. Particularly, it is preferable that the absorbance at 308 nm and 355 nm is high.

Specific examples of the organic halogenated compound include Wakabayashi et al., "Bull Chem. Soc. Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48 -36281, JP 55-32070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62 -58241, Japanese Patent Laid-Open No. 62-212401, Japanese Patent Laid-Open No. 63-70243, Japanese Patent Laid-Open No. 63-298339, MPHutt "Journal of Heterocyclic Chemistry" 1 (No3), (1970 And the like, and the oxazole compound in which the trihalomethyl group is substituted, and the s-triazine compound.

As an example of a hexaaryl biimidazole compound, the various compounds described in each specification, such as Unexamined-Japanese-Patent No. 6-29285, US Patent 3,479,185, 4,311,783, 4,622,286, specifically, are mentioned, for example. 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl)) 4,4', 5, 5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chloro Phenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 ' -Tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4, 4 ', 5,5'- tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4', 5,5'- tetraphenylbiimidazole, etc. are mentioned.

The photopolymerization initiator may be used alone or in combination of two or more. When two or more compounds are used, a plurality of compounds represented by formula (B) may be used, or a plurality of compounds represented by formula (II) may be used. Moreover, you may use at least 1 sort (s) from the compound represented by general formula (II) and general formula (III), respectively. Moreover, photopolymerization other than an oxime compound or an oxime compound other than the compound represented by at least 1 sort (s), a general formula (II), and a general formula (III) is respectively represented by general formula (II) and general formula (III). You may use an initiator. A sensitizer may also be used in combination.

It is preferable that the total content of a photoinitiator is 0.1 mass%-20 mass% with respect to the total solid in a coloring photosensitive composition, It is more preferable that it is 0.5 mass%-20 mass%, and 1 mass%-10 mass% are the most preferable. . Within this range, sensitivity at the time of exposure is high and color characteristics are good.

&Lt; (E) Alkali soluble binder >

In the colored photosensitive composition of the present invention, it is preferable to use an alkali-soluble binder from the viewpoint of improving the film formability and also from the viewpoint of pattern formation.

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

The alkali-soluble binder is preferably a linear organic high polymer, soluble in an organic solvent, and capable of being developed with a weak alkaline aqueous solution. Examples of such linear organic polymers include polymers having a carboxylic acid in the side chain, such as Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication 54 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, males as described in the Japanese Unexamined Patent Publication Nos. 59-53836 and 59-71048 Acid copolymers, partially esterified maleic acid copolymers, and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are likewise useful.

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

Moreover, an alkali-soluble binder may have a polymeric group in a side chain in order to improve crosslinking efficiency, For example, the polymer etc. which contain an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in a side chain are also useful. As an example of the polymer containing the above-mentioned polymerizable group, Diamond NR series (made by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH containing polyurethane acrylic oligomer. Product of Diamond Shamrock Co. Ltd., Biscot R-264, KS resist 106 (all made by Osaka Yuki Kagaku Kogyo Co., Ltd.), cyclomer P series, Fraxel CF200 series (all made by Daicel Kagaku Kogyo Co., Ltd.), Ebecryl 3800 (manufactured by Daicel Yusubishi Co., Ltd.) Can be mentioned. Further, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured coating.

Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxy styrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acryl / acrylamide copolymer resin are preferable, and acrylic resin from the viewpoint of developability control. , Acrylamide resins and acryl / acrylamide copolymer resins are preferred.

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

The alkali-soluble binder preferably has a polymer having a weight average molecular weight (polystyrene equivalent value measured by the GPC method) of 1000 to 2 × 10 ⁵ from the viewpoint of developability, liquid viscosity, and the like, and more preferably 2000 to 1 × 10 ⁵ . And, the polymer of 5000-5 * 10 <^4> is especially preferable. Two or more species may be used alone or in combination.

<Other ingredients>

If necessary, the coloring photosensitive composition of the present invention may also contain known additives such as polyfunctional thiol compounds, chain transfer agents, polymerization inhibitors, organic solvents, surfactants, and adhesion improving agents, as long as the effects of the present invention are not impaired. , Crosslinking agents, development accelerators, and other additives.

These components are demonstrated below.

(Polyfunctional thiol compound)

The colored photosensitive composition of the present invention may contain a polyfunctional thiol compound.

When the coloring photosensitive composition of this invention improves a sensitivity by containing a polyfunctional thiol compound, ion elution, etc. resulting from color materials, such as dye, is suppressed, and when the coloring photosensitive composition of this invention is used for the color filter preparation of a liquid crystal display device, Deterioration of image quality such as crosstalk can be prevented, and clear high quality display is possible.

In the present invention, the "polyfunctional thiol compound" means a compound having two or more thiol groups in the molecule. As the polyfunctional thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight is preferably 100 to 1,500, more preferably 150 to 1,000. The polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, more preferably 2 to 6. Moreover, it is preferable to make these compounds into the system used auxiliary | assistant when the said radically polymerizable monomer superposes | polymerizes. Specifically, the addition amount of the polyfunctional thiol compound is preferably 1 to 20% by mass based on the total solid content of the composition, or the added amount is smaller than the addition amount of the radically polymerizable monomer contained at the same time.

As a specific example of the polyfunctional thiol compound which can be used for this invention, a trimethol propane tris (3-mercapto propionate), pentaerythritol tetrakis (3- mercapto propionate), tetraethylene glycol bis is mentioned, for example. (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptobutylate), butanediol bis (3-mercaptobutylate), 1,4-bis (3-mercaptobutyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- 2,4,6 (1H, 3H, 5H) -trione etc. are mentioned as a suitable polyfunctional thiol compound.

The content of the polyfunctional thiol compound is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total solid content in the colored photosensitive composition. When content of a polyfunctional thiol compound exists in this range, the sensitivity of a coloring photosensitive composition is favorable, storage stability is favorable, adhesiveness of the pixel in the obtained color filter is favorable, there is no pattern defect, and when used for a liquid crystal display device It is possible to provide a colored photosensitive composition having good electrical properties.

(Sensitizer)

A sensitizer may be added to the colored photosensitive composition of the present invention. Typical sensitizers for use in the present invention include Krivelo [J.V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)], specifically, pyrene, perylene, acridine, thioxanthone, 2-chloro thioxanthone, benzoflavin, N-vinyl Carbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphaquinone, phenothiazine derivatives, and the like. The sensitizer is preferably added in a proportion of 50 to 200 mass% with respect to the photopolymerization initiator.

(Chain transfer agent)

A chain transfer agent can also be added to the coloring photosensitive composition of this invention. Examples of the chain transfer agent used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, The mercapto compound which has heterocycles, such as 2-mercapto benzoimidazole and N-phenyl mercapto benzoimidazole, etc. are mentioned.

A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

The addition amount of the chain transfer agent is preferably in the range of 0.01 to 15% by mass with respect to the total solids of the colored photosensitive composition of the present invention from the viewpoint of reducing the sensitivity unevenness, more preferably 0.1 to 10% by mass, and 0.5 to 5% by mass. % Is particularly preferred.

(No Polymerization)

The coloring photosensitive composition of this invention may contain a polymerization inhibitor.

The polymerization inhibitor is a hydrogen donor (or hydrogen donor), an energy donor (or an energy donor), an electron donor (or an electron donor), or the like, for a polymerization initiation species such as radicals generated in a colored photosensitive composition by light or heat. It is a substance which inactivates a starting species and suppresses initiation of polymerization unintentionally. The polymerization inhibitor of Paragraph 0154 of Unexamined-Japanese-Patent No. 2007-334322-0173, etc. can be used.

Among these, p-methoxyphenol is mentioned preferably as a polymerization inhibitor.

As for content of the polymerization inhibitor in the coloring photosensitive composition of this invention, 0.0001-5 mass% is preferable with respect to the total mass of a polymeric compound, 0.001-5 mass% is more preferable, 0.001-1 mass% is especially preferable. Do.

[(F) Organic Solvent]

It is preferable that the coloring photosensitive composition of this invention contains the (F) organic solvent.

Moreover, it is preferable that the dispersion composition in this invention contains the (F) organic solvent.

The organic solvent contained in the dispersion composition and the organic solvent contained in the colored photosensitive composition may be the same kind or different kinds, or the organic solvent contained in the dispersed composition and the colored photosensitive composition may be one kind or two or more kinds. good.

The organic solvent (F) is not particularly limited as long as it can satisfy the solubility of each component to be coexisted and the coating property when the colored photosensitive composition is used, and in particular, the organic solvent is selected in consideration of solubility, coating property and safety of solid content. It is preferable.

(F) Examples of the organic solvent include esters such as ethyl acetate, acetic acid-n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate and butyl butyrate, Methyl lactate, ethyl lactate, alkyl oxyacetates (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically methyl methoxyacetate, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, Ethyl oxyacetate, etc.)), 3-oxypropionic acid alkylesters, 2-oxypropionic acid alkylesters, 2-oxy-2-methylpropionate methyl, 2-oxy-2-methylpropionate ethyl, pyruvate methyl Ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, methyl 2-oxobutane, 2-oxobutane And ethyl ethyl.

Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, di Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate. have.

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

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

When these organic solvents contain the solubility of each component mentioned above, and an alkali-soluble binder, it is also preferable to mix 2 or more types from a viewpoint of the solubility, the improvement of a coated surface shape, etc. In this case, particularly preferable examples thereof include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, butyl acetate, 3- Is a mixed solution composed of two or more kinds selected from methyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

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

(Surfactants)

The colored photosensitive composition of the present invention may contain a surfactant.

As the surfactant, any of anionic, cationic, nonionic, and amphoteric compounds can be used, but preferred surfactants are nonionic surfactants. Specific examples include the nonionic surfactants described in paragraph 0058 of Japanese Patent Application Laid-Open No. 2009-098616, and among them, fluorinated surfactants are preferred.

As other surfactant which can be used for this invention, a commercially available mega pack F142D, copper F172, copper F173, copper F176, copper F177, copper F183, copper F479, copper F482, copper F554, copper F780, copper F781 , F781-F, copper R30, copper R08, copper F-472SF, copper BL20, copper R-61, copper R-90 (above, manufactured by DIC Corporation), fluoride FC-135, copper FC-170C, East FC-430, East FC-431, Novec FC-4430 [above, made by Sumitomo Industries Co., Ltd.], Asahi Guard AG 7105, 7000, 950, 7600, Saffron S-112, East S-113, East S -131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 Asahi Glass Co., Ltd.], F-Top EF351, 352, 801, 801, above 802 (above, Mitsubishi Material Denshi Kasei Co., Ltd. product), Pgentent 250 [neos Co., Ltd. product] etc. are mentioned. .

Moreover, the weight average molecular weight (Mw) of polystyrene conversion measured by gel permeation chromatography with the structural unit A and structural unit B represented by a following formula (W) as a solvent, and using tetrahydrofuran as a solvent is 1,000. The copolymer more than 10,000 is mentioned as a preferable example.

(In formula (W), R <^1> and R <^3> respectively independently represents a hydrogen atom or a methyl group, R <^2> represents a C1-C4 straight alkylene group, R <^4> represents a hydrogen atom or C1-C4 An alkyl group is represented, L is a C3-C6 alkylene group, p and q are the mass percentages which show a polymerization ratio, p represents the numerical value of 10 mass% or more and 80 mass% or less, q is 20 mass The numerical value of% or more and 90 mass% or less is shown, R shows the integer of 1 or more and 18 or less, n represents the integer of 1 or more and 10 or less.)

It is preferable that L is a branched alkylene group represented by the following formula (W-2). R ⁵ in the formula (W-2) represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a surface to be coated, and an alkyl group having 2 or 3 carbon atoms More preferable.

The sum (p + q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

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

The amount of the surfactant to be added to the colored photosensitive composition of the present invention is preferably 0.01 to 2.0% by mass, more preferably 0.02 to 1.0% by mass, based on the total solid content of the colored photosensitive composition. If it is this range, applicability | paintability and the uniformity of a cured film become favorable.

(Adhesive modifier)

The colored photosensitive composition of the present invention may contain an adhesion improver.

The adhesion improver is a compound that improves the adhesion of an inorganic substance as a support, for example, glass, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a cured film of gold, copper, aluminum, or the like. Specific examples thereof include silane coupling agents. The silane coupling agent as the adhesion improver is for the purpose of modifying the interface and is not particularly limited and a known silane coupling agent can be used.

As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A No. 2009-98616 is preferable, and among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable. These may be used singly or in combination of two or more.

The content of the adhesion improver in the colored photosensitive composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the colored photosensitive composition.

(Crosslinking agent)

The hardness of the colored layer formed by hardening a colored photosensitive composition can also be raised more, using a crosslinking agent supplementally to the colored photosensitive composition of this invention.

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

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

(Developing accelerator)

When promoting the alkali solubility of the non-exposed area | region at the time of exposing a coloring photosensitive composition layer, and for the further improvement of the developability of a coloring photosensitive composition, you may add a development accelerator. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less, or a low molecular weight phenolic compound having a molecular weight of 1000 or less.

Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl Aliphatic dicarboxylic acids such as succinic acid and citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melotropic acid and pyromellitic acid; And phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamylidene acetic acid, kumaric acid, and umbelic acid.

(Other additives)

Various additives, for example, a filler, a high molecular compound other than the above, an ultraviolet absorber, antioxidant, etc. can be mix | blended with the coloring photosensitive composition of this invention as needed. Examples of these additives include those described in paragraphs [0155] to [0156] of Japanese Patent Application Laid-Open No. 2004-295116.

In the coloring photosensitive composition of this invention, the light stabilizer of Paragraph [0078] of Unexamined-Japanese-Patent No. 2004-295116, and the thermal polymerization inhibitor of Paragraph [0081] of the said publication can be contained.

(Method for preparing colored photosensitive composition)

The colored photosensitive composition of the present invention is prepared by mixing the respective components described above with optional components as required. Preferably, the above-mentioned dispersion composition is used as the coloring agent component, and the above-mentioned respective components are mixed with optional components as required.

In addition, at the time of preparation of a coloring photosensitive composition, each component which comprises a coloring photosensitive composition may be mix | blended collectively, and may be mix | blended sequentially. In addition, the addition order and working conditions at the time of compounding are not restrict | limited.

The coloring photosensitive composition prepared as mentioned above, Preferably, it can filter and select using a filter of about 0.01 micrometer-about 3.0 micrometers, etc., and can use it for use.

Since the colored photosensitive composition of this invention can form the colored cured film excellent in heat resistance and excellent contrast, it is used for formation of colored pixels, such as a color filter used for a liquid crystal display device, and also manufactures a printing ink, an inkjet ink, a paint, etc. It can be used suitably as a use.

<< color filter and manufacturing method thereof >>

The color filter of this invention is formed by forming the coloring region which consists of a coloring photosensitive composition of this invention on a support body and the said support body. The colored region on the support is composed of colored layers, such as red (R), green (G), and blue (B), which constitute each pixel of the color filter.

The manufacturing method of the color filter of this invention provides about the colored layer formation process (A) which gives the above-mentioned colored photosensitive composition on a support body, and forms a colored layer (colored photosensitive composition layer), and the colored layer formed in process (A). An exposure step (B) for exposing the pattern shape and a developing step (C) for developing the exposed colored layer to form a colored pattern.

Moreover, in the manufacturing method of the color filter of this invention, the aspect which provided further the process (D) which heat-processes especially the coloring pattern obtained at the process (C) is preferable.

Hereinafter, the manufacturing method of the color filter of this invention is demonstrated more concretely.

Process (A)

In the manufacturing method of the color filter of this invention, the coloring layer of the above-mentioned coloring photosensitive composition of this invention is first given to application | coating methods, such as rotation coating, slit coating, casting | coating, roll coating, bar coating, and inkjet, on a support body. After that, the colored layer is dried by heating (prebaking) or vacuum drying.

As a support body, the soda glass, alkali free glass, borosilicate glass, quartz glass, a silicon substrate, a resin substrate, etc. which are used for a liquid crystal display device are mentioned, for example. Moreover, on these support bodies, you may form an undercoat layer as needed for the contact improvement of an upper layer, the prevention of the diffusion of a substance, or the planarization of a surface.

Examples of the prebaking conditions include heating at 70 to 130 캜 for about 0.5 to 15 minutes using a hot plate or an oven.

In addition, the thickness of the colored layer formed by the colored photosensitive composition is appropriately selected according to the purpose. In the color filter for liquid crystal display devices, the range of 0.2 micrometer-5.0 micrometers is preferable, and the range of 1.0 micrometer-4.0 micrometers is more preferable. In addition, the thickness of a colored layer is the film thickness after drying.

Process (B)

Subsequently, in the manufacturing method of the color filter of this invention, exposure of pattern shape is performed with respect to the colored layer formed on the support body. As the light or radiation applicable to exposure, g-line, h-line, i-line and various laser beams are preferable, and i-line is particularly preferable. When using a high pressure mercury lamp for irradiation light, it is preferable to irradiate with the exposure amount of 5mJ / cm <2> -500mJ / cm <2>.

As other exposure light sources, various high pressure, high pressure, medium and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, and various laser light sources can be used.

~ Exposure process using laser light source ~

In the exposure system using a laser light source, the ultraviolet light laser of the wavelength range whose wavelength is 300 nm-410 nm is preferable, More preferably, it is a wavelength which is the range of 300 nm-360 nm. Specifically, the third harmonic (355 nm) of the Nd: YAG laser of a solid laser having a large output and relatively low cost, and XeCl (308 nm) and XeF (353 nm) which are excimer lasers can be suitably used. The pattern exposure dose is preferably in the range of 1 mJ / cm 2 to 100 mJ / cm 2, more preferably in the range of 1 mJ / cm 2 to 50 mJ / cm 2 from the viewpoint of productivity.

Although there is no restriction | limiting in particular as an exposure apparatus, Callisto (made by V Technology Corp.), EGIS (made by V Technology Corp.), DF2200G (made by Dainippon Screen Corp.), etc. can be used as a commercially available thing. Moreover, the apparatus of that excepting the above is also used suitably.

- Process (C) -

Then, image development is performed with a developing solution with respect to the colored layer after exposure. Thereby, a coloring pattern can be formed. As long as the developing solution melt | dissolves the unhardened part of a colored layer and does not melt a hardened part, the combination of various organic solvents and alkaline aqueous solution can be used. When the developing solution is an alkaline aqueous solution, it is preferable to adjust so that alkali concentration may become pH10-13 preferably. As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium, for example. And alkaline aqueous solutions such as hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene.

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

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

Moreover, after image development using alkaline aqueous solution, it is preferable to wash with water.

In the manufacturing method of the color filter of this invention, it is also especially preferable to perform post-exposure by ultraviolet irradiation with respect to the coloring pattern (pixel) formed using the coloring photosensitive composition.

- Process (D) -

It is preferable to heat-process further about the coloring pattern after image development, or the coloring pattern in which postexposure by the above-mentioned ultraviolet irradiation was performed. The coloring pattern formed can be further cured by heat treatment (so-called post-baking treatment). This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.

As temperature at the time of heat processing, it is preferable that it is 100 degreeC-300 degreeC, More preferably, it is 150 degreeC-250 degreeC. Moreover, as for heating time, about 10 to 120 minutes are preferable.

The coloring pattern thus obtained constitutes a blue pixel in the color filter. In preparation of the color filter which has a pixel of multiple colors, the said process (A), a process (B), a process (C), and a process (D) may be repeated according to the desired number of colors.

In addition, the said process (D) may be performed whenever formation, exposure, and image development of a monochromatic color layer are complete | finished (for every one color), and it is collectively after formation, exposure, and image development of all the color layers of desired color number are complete | finished. You may perform the said process (D).

Further, the colored photosensitive composition of the present invention can form a blue colored layer to form a blue pixel on the support. However, when the colored pixel is composed of red blue green, the order of forming the colored layer may be in any order.

<< display device >>

Since the color filter (color filter of this invention) obtained by the manufacturing method of the color filter of this invention uses the coloring photosensitive composition of this invention, it is excellent in heat resistance and contrast.

The display device of the present invention includes the color filter of the present invention.

As the display device of the present invention, specifically, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a mobile terminal such as a mobile phone, a digital camera Display devices such as a display device for a car and a display device for a car navigation device are particularly suitable.

When the color filter of this invention is used for an organic electroluminescent display, a liquid crystal display, etc., display of the image excellent in spectral characteristics and contrast is attained, achieving favorable hue.

<LCD display device>

The liquid crystal display device using the color filter of this invention is demonstrated. About definition of organic EL display device and liquid crystal display device and the detail of each display device, for example, "electronic display device (Seraki Teruo, Japan High School Chosaka 1990 issuance)", "display device (Sumi Ibuki) Archer, Sankyo Show Co., Ltd., published in 1989). In addition, the liquid crystal display device is described, for example, in "next-generation liquid crystal display technology (Tatsuo Uchida editorial, 1994 issued by High School Chosaka Co., Ltd.)." There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology."

The color filter of the present invention is particularly effective for a color TFT type liquid crystal display device. About the liquid crystal display device of a color | collar TFT system, it describes in a "color TFT liquid crystal display (Kyoritsu Shootpan Co., Ltd. 1996 issuance), for example." In addition, the present invention can be applied to liquid crystal display devices having an enlarged viewing angle, such as a transverse electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. . In addition, the color filter of the present invention can be provided in a color-filter on array (COA) method.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a three-wavelength tube of a conventionally known cold cathode tube, but the luminance is achieved by using red, green, and blue LED light sources (RGB-LEDs) as backlights. It is possible to provide a liquid crystal display device having high color reproducibility and high color purity.

[Example]

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples. In addition, "%" "part" is a mass reference | standard unless there is particular notice.

Example 1

Preparation of Blue Dispersion Composition 1

&Lt; Preparation of color material composition &

100 parts of commercial CI pigment blue 15: 6 (product name: FICGEN BLUE EP193 by DIC Corporation), 50 parts of dye (exemplary compound 1 of the dye), 400 parts of sodium chloride, and 140 parts of water-soluble organic solvent diethylene glycol It was put in the brother kneader (made by Shokai Irie Co., Ltd.) and kneaded for 10 hours. Subsequently, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nihon Seiki Seisakusho Co., Ltd.), filtered, washed with water, and sodium chloride and solvent were removed to obtain a color cake. Thereafter, this male cake was dried in an oven at 80 ° C. for 6 hours to obtain a colorant composition of C.I. Pigment Blue 15: 6 and a dye.

Crude dispersal

After combining with the following composition using the said color material composition, the mixture was disperse | distributed using Eiger Mill (made by Eiger Japan Co., Ltd.) and zirconia beads of 0.8 mm in diameter.

Color composition: 150 parts

Pigment derivative (I) (following structure): 10 parts

Polymeric dispersant (exemplary compound 1 below): 80 parts

Propylene glycol monomethyl ether acetate: 260 parts

In addition, the pigment derivative (I) was synthesize | combined according to the method of Paragraph 0056 of Unexamined-Japanese-Patent No. 2003-253078. CuPc in the following structural formula represents a copper phthalocyanine residue. In addition, Exemplary Compound 1 was synthesized according to the method described in JP 2011-178865 A.

Pigment Derivatives (I)

<Precision dispersion>

The dispersion after the said crude dispersion was taken out, 30 parts of propylene glycol monomethyl ether acetates were added and mixed with respect to 100 parts of dispersion. Then, it disperse | distributed using Eiger Mill (made by Eiger Japan Co., Ltd.) and zirconia beads of diameter 0.1mm.

<Concentration adjustment>

The dispersion after precision dispersion was taken out, propylene glycol monomethyl ether acetate was added and diluted so that a pigment concentration might be 10%, and it was set as the blue dispersion composition 1.

- Preparation of colored photosensitive compositions -

Each following component was mixed and dissolved, and the coloring photosensitive composition 1 was prepared.

Organic solvent 1: 33 parts of propylene glycol monomethyl ether acetate

Organic solvent 2: 26 parts of diethylene glycol ethyl methyl ether

Alkali-soluble binder 1: Addition of methacrylic acid (45% propylene glycol monomethyl ether solution) of cyclohexyl methacrylate / methacrylic acid / glycidyl methacrylate (= molar ratio: 30/30/40) 4 part

Alkali-soluble binder 2: Allyl methacrylate / methacrylic acid copolymer = 4 parts of molar ratio 70/30 (weight average molecular weight 26800)

Polymerizable compound 1: Nippon Kayaku Co., Ltd., KAYARAD DPHA 3 parts

Polymerizable compound 2: Toagosei Co., Ltd., Aaronics TO-2349 3 parts

Polymerization inhibitor: 0.003 parts of p-methoxyphenol

Photoinitiator 1: 0.3 part of 1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone

Photoinitiator 2: 1 part of 1,3-dihydro-1-phenyl-2H-benzimidazole-2-thione)

Polyfunctional thiol compound: 0.1 part of 1,4-bis (3-mercaptobutyryloxy) butane

Adhesion improver: 0.2 part of 3-methacryloxypropyl trimethoxysilane)

Fluorine-based surfactant: 5 parts Megapack F-554 (0.2% propylene glycol monomethyl ether acetate solution) manufactured by DIC Corporation

Blue dispersion composition 1 30 parts

EXAMPLES 2-6

The coloring photosensitive compositions 2-6 were created like Example 1 except having changed the dye used at the time of preparation of a color material composition in Example 1 as shown in Table 1.

[Example 7]

Preparation of Blue Dispersion Composition 7

<Minification of Pigment>

100 parts of commercially available C.I. Pigment Blue 15: 6 used in Example 1, 400 parts of sodium chloride, and 140 parts of diethylene glycol were charged to a table-type kneader (manufactured by Irishokai Co., Ltd.), and kneaded for 10 hours. Subsequently, this kneaded product was stirred and mixed with water in a dissolver (manufactured by Nihon Seiki Seisakusho Co., Ltd.), filtered and washed repeatedly to remove sodium chloride and a solvent, thereby obtaining a colored cake of color material. This male cake was then dried in an oven at 80 ° C. for 6 hours to obtain a micronized pigment of C.I. Pigment Blue 15: 6.

Crude dispersal

After combining with the following composition using the said refinement | miniaturization pigment, the mixture was disperse | distributed using Eiger Mill (made by Eiger Japan Co., Ltd.) and zirconia beads of 0.8 mm in diameter.

100 parts of fine pigment

Dye: 667 parts of exemplary compound 1 (7.5% propylene glycol monomethyl ether acetate solution) of the dye

Pigment derivative (I) 10 parts

Polymeric dispersant: 80 parts of exemplary compound 1

Propylene glycol monomethyl ether acetate: 40 parts

<Precision dispersion>

The dispersion after the said crude dispersion was taken out, and after that, it disperse | distributed using Eiger Mill (made by Eiger Japan Co., Ltd.) and zirconia beads of diameter 0.1mm.

<Concentration adjustment>

The dispersion after the said fine dispersion was taken out, propylene glycol monomethyl ether acetate was added and diluted so that a pigment concentration might be 10%, and it was set as the blue dispersion composition 7.

Preparation of the colored photosensitive composition 7

In Example 1, the coloring photosensitive composition 7 was produced like Example 1 except having changed the blue dispersion composition 1 into the blue dispersion composition 7.

[Examples 8 to 12]

Colored photosensitive compositions 8-12 were created like Example 7 except having changed the dye added by the crude dispersion in Example 7 as shown in Table 1.

[Example 13]

Preparation of Blue Dispersion Composition 13

<Minification of Pigment>

100 parts of commercially available C.I. Pigment Blue 15: 6 used in Example 1, 400 parts of sodium chloride, and 140 parts of diethylene glycol were charged to a table-type kneader (manufactured by Irishokai Co., Ltd.), and kneaded for 10 hours. Subsequently, this kneaded product was stirred and mixed with water in a dissolver (manufactured by Nihon Seiki Seisakusho Co., Ltd.), filtered, washed with water, and sodium chloride and solvent were removed to obtain a color cake. This male cake was then dried in an oven at 80 ° C. for 6 hours to obtain a micronized pigment of C.I. Pigment Blue 15: 6.

Crude dispersal

After combining with the following composition using the said refinement | miniaturization pigment, the mixture was disperse | distributed using Eiger Mill (made by Eiger Japan Co., Ltd.) and zirconia beads of 0.8 mm in diameter. At that time, the micronized pigment and the dye were first mixed in a powder state, and then other materials were added and dispersed.

100 parts of fine pigment

Dye: 50 parts of exemplary compound of dye

Pigment derivative (I) 10 parts

Polymeric dispersant: 80 parts of exemplary compound 1

Propylene glycol monomethyl ether acetate 260 parts

<Precision dispersion>

The dispersion after the said crude dispersion was taken out, 30 parts of propylene glycol monomethyl ether acetates were added and mixed with respect to 100 parts of dispersion. Then, it disperse | distributed using Eiger Mill (made by Eiger Japan Co., Ltd.) and zirconia beads of diameter 0.1mm.

<Concentration adjustment>

The dispersion composition after the said precise dispersion was taken out, propylene glycol monomethyl ether acetate was added and diluted so that a pigment concentration might be 10%, and it was set as the blue dispersion composition 13.

Preparation of the colored photosensitive composition 13

In Example 1, the coloring photosensitive composition 13 was produced like Example 1 except having changed the blue dispersion composition 1 into the blue dispersion composition 13.

[Examples 14-18]

Colored photosensitive compositions 14-18 were created like Example 13 except having changed the dye added in the crude dispersion in Example 13 as shown in Table 1.

[Example 19]

Preparation of Blue Dispersion Composition 19

<Minification of Pigment>

100 parts of commercially available C.I. Pigment Blue 15: 6 used in Example 1, 400 parts of sodium chloride, and 140 parts of diethylene glycol were charged to a table-type kneader (manufactured by Irishokai Co., Ltd.), and kneaded for 10 hours. Subsequently, this kneaded product was stirred and mixed with water in a dissolver (manufactured by Nihon Seiki Seisakusho Co., Ltd.), filtered, washed with water, and sodium chloride and solvent were removed to obtain a color cake. This male cake was then dried in an oven at 80 ° C. for 6 hours to obtain a micronized pigment of C.I. Pigment Blue 15: 6.

Crude dispersal

Using the said refinement | miniaturization pigment, after combination with the following composition, the mixture was disperse | distributed using Eiger Mill (made by Eiger Japan Co., Ltd.) and zirconia beads of 0.8 mm in diameter.

100 parts of fine pigment

Pigment derivative (I) 10 parts

Polymeric dispersant: 80 parts of exemplary compound 1

Propylene glycol monomethyl ether acetate 260 parts

<Precision dispersion>

The dispersion after the above dispersion was taken out, and 11 parts of Exemplary Compound 1 of the dye was added and mixed with 100 parts of the dispersion. Then, 30 parts of propylene glycol monomethyl ether acetates were added, and it disperse | distributed using Eiger Mill (made by Eiger Japan Co., Ltd.) and zirconia beads of diameter 0.1mm.

<Concentration adjustment>

The dispersion composition after the said precise dispersion was taken out, the propylene glycol monomethyl ether acetate was added and diluted so that the pigment concentration might be 10%, and it was set as the blue dispersion composition 19.

Preparation of the colored photosensitive composition 19

In Example 1, the coloring photosensitive composition 19 was produced like Example 1 except having changed the blue dispersion composition 1 into the blue dispersion composition 19.

[Examples 20 to 24]

Colored photosensitive compositions 20-24 were created like Example 19 except having changed the dye added at the time of fine dispersion in Example 19, as described in Table 1.

Comparative Example 1

Preparation of Blue Dispersion Composition A

<Minification of Pigment>

100 parts of commercially available C.I. Pigment Blue 15: 6 used in Example 1, 400 parts of sodium chloride, and 140 parts of diethylene glycol were charged to a table-type kneader (manufactured by Irishokai Co., Ltd.), and kneaded for 10 hours. Subsequently, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nihon Seiki Seisakusho Co., Ltd.), filtered, washed with water, sodium chloride and solvent were removed, and a colored cake was obtained. This male cake was then dried in an oven at 80 ° C. for 6 hours to obtain a micronized pigment of C.I. Pigment Blue 15: 6.

Crude dispersal

Using the said refinement | miniaturization pigment, after combination with the following composition, the mixture was disperse | distributed using Eiger Mill (made by Eiger Japan Co., Ltd.) and zirconia beads of 0.8 mm in diameter.

100 parts of fine pigment

Pigment derivative (I) 10 parts

Polymeric dispersant: 80 parts of exemplary compound 1

Propylene glycol monomethyl ether acetate 260 parts

<Precision dispersion>

The dispersion after the above dispersion was taken out, and 100 parts of the dispersion and 125 parts of Exemplary Compound 1 (9% solution of propylene glycol monomethyl ether acetate) as a dye were mixed. Then, it disperse | distributed using Eiger Mill [made by Eiger Japan Co., Ltd.] and zirconia bead of diameter 0.1mm, and obtained blue dispersion composition A of 10% of pigment concentration.

- Preparation of colored photosensitive composition A -

The coloring photosensitive composition A was produced like Example 1 except having changed the blue dispersion composition 1 into the blue dispersion composition A in Example 1.

Comparative Example 2

Preparation of Blue Dispersion Composition B

<Minification of Pigment>

100 parts of commercially available C.I. Pigment Blue 15: 6 used in Example 1, 400 parts of sodium chloride, and 140 parts of diethylene glycol were charged to a table-type kneader (manufactured by Irishokai Co., Ltd.), and kneaded for 10 hours. Subsequently, this kneaded product was stirred and mixed with water in a dissolver (manufactured by Nihon Seiki Seisakusho Co., Ltd.), filtered, washed with water, and sodium chloride and solvent were removed to obtain a color cake. This male cake was then dried in an oven at 80 ° C. for 6 hours to obtain C.I. Pigment Blue 15: 6.

Crude dispersal

Using the said refinement | miniaturization pigment, after combination with the following composition, the mixture was disperse | distributed using Eiger Mill (made by Eiger Japan Co., Ltd.) and zirconia beads of 0.8 mm in diameter.

100 parts of fine pigment

10 parts of pigment derivative (I) described in Japanese Patent Laid-Open No. 2011-178865.

80 parts of polymer dispersant (example compound A)

Propylene glycol monomethyl ether acetate 260 parts

<Precision dispersion>

The dispersion after the said crude dispersion was taken out, and 19 parts of propylene glycol monomethyl ether acetates were added and mixed with respect to 100 parts of dispersion. Then, it disperse | distributed using Eiger Mill (made by Eiger Japan Co., Ltd.) and zirconia beads of diameter 0.1mm. After dispersion, 11 parts of dye (exemplary compound 1 of the dye) were added and mixed with a Three One motor to obtain a blue dispersion composition B.

Preparation of the colored photosensitive composition B

The colored photosensitive composition B was produced like Example 1 except having changed the blue dispersion composition 1 into the blue dispersion composition B in Example 1.

[Comparative Example 3]

Preparation of Blue Dispersion Composition C

After combining with the following composition, the mixture was disperse | distributed using the paint shaker (made by Seiwa Kiken) and zirconia beads of diameter 0.1mm, and blue dispersion composition C was obtained.

100 parts of commercial C.I.Pigment Blue 15: 6 used in Example 1

50 parts of exemplary compound 1

Pigment derivative (I) 10 parts

80 parts of polymer dispersant (example compound 1)

Propylene glycol monomethyl ether acetate 760 parts

- Preparation of colored photosensitive composition C -

The coloring photosensitive composition C was produced like Example 1 except having changed the blue dispersion composition 1 into the blue dispersion composition C in Example 1.

Thus, Ci and Cf in the coloring photosensitive composition produced are shown below.

Ci in Examples 1-6 is calculated from the density | concentration of the specific dye at the time of premixing, and it is all 33.3%, Cf is calculated from the density | concentration of the dye in the dispersion composition after concentration adjustment after completion | finish of dispersion, and Example 1 In Example 6, all were 5.0%.

In addition, Ci in Examples 7-18 is calculated from the composition of crude dispersion. All Ci of Example 7-12 is 5.5%, and all Ci of Example 13-18 is 10%. Cf is calculated from the density | concentration of the dye in the dispersion composition after concentration adjustment after completion | finish of dispersion, and in Example 7-18, it is all 5.0%.

In Examples 19 to 24, Ci is calculated from the composition of the fine dispersion and is all 7.8%, and Cf is calculated from the concentration of the dye in the dispersion composition after the concentration adjustment after completion of the dispersion, and all are 5.0%.

In Comparative Examples 1 to 3, all are Ci = Cf, and both are 5.0%.

-evaluation-

As performance evaluation of the coloring photosensitive compositions 1-24 and A-C obtained above, the spectral characteristic, contrast, and heat resistance were evaluated by the method shown below. Moreover, the dye adsorption rate to the pigment in each blue-blue dispersion composition was also evaluated simultaneously. The evaluation results are shown in Table 1 below.

- Formation of colored photosensitive composition layer (colored layer)

The colored photosensitive composition prepared above was coated on a glass substrate (made by Corning Inc.) by spin coating and dried at room temperature for 30 minutes to volatilize the volatile components to form a colored layer. This colored layer was irradiated with i line | wire (wavelength 365nm) through the mask of a thin wire pattern, and the latent image was formed. An ultra-high pressure mercury lamp was used as the i-line light source and irradiated after being made into parallel light. At this time, the irradiation light amount was 40 mJ / cm 2. Subsequently, the latent image-formed colored layer was developed for 45 seconds at 26 ° C. using an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%), followed by rinsing with flowing water for 20 seconds, followed by drying with a spray, to obtain a thin wire pattern image. . The obtained thin wire pattern image was post-baked at 230 degreeC for 20 minutes, and the colored layer which has a blue fine wire pattern with a film thickness of 2 micrometers was obtained.

(Contrast evaluation)

The value of the brightness | luminance in the case where the polarizing axis of two polarizing films is parallel, and when the polarizing axis of two polarizing films is parallel is sandwiched between the board | substrates which have the obtained colored layer, and a color luminance meter (made by Topcon Co., Model No .: BM -5A], and the value obtained by dividing the brightness | luminance in case the polarization axis of two polarizing films is parallel by the brightness | luminance in case of vertical was calculated | required as contrast. The higher the contrast, the better the color filter for the liquid crystal display device.

(Spectral characteristics)

The transmission spectrum of the colored layer obtained above was measured using the microscopic spectrometer (Olympus Co., Model No. OSP-SP200). From the obtained transmission spectrum, the chromaticity coordinate x value, y value and Y value in the CIE 1931 color coordinate system were determined.

It can be said that the spectral characteristics have excellent spectral characteristics as the Y value at (x, y) = (0.138, 0.085) is larger.

(Heat resistance)

After the transmission spectrum of the colored layer obtained above was measured using a microscopic spectrometer (Olympus Co., Ltd., model number OSP-SP200), further baking was performed at 230 degreeC for 60 minutes, and the transmission spectrum was evaluated again. Y value difference ((DELTA) Y) before and after further baking was computed, and this was made into the heat resistance index. It can be said that the smaller ΔY is, the better the heat resistance is.

(Dye adsorption rate)

Each blue dispersion composition was centrifuged with a ultracentrifuge (manufactured by Hitachi Koki Co., Ltd.) 50000 rpm to obtain a supernatant liquid containing a free component. In addition, the ultracentrifugal separator used for the said centrifugal process was made into CS150GX (made by Hitachi Koki Co., Ltd.), The centrifugal capacity was 1 g, and the centrifugal time (it may vary with a sample) is generally about 1 to 6 hours. The amount of dye in supernatant was evaluated by HPLC, and the adsorption rate (%) was defined by the following formula.

From the results in Table 1, the following can be said. Colored photosensitive compositions 1-24 of this invention have the outstanding heat resistance with respect to the colored photosensitive compositions A-C of a comparative example. Since heat resistance correlates with dye adsorption rate, it is estimated that heat discoloration is suppressed by dye adsorb | sucking to a pigment. Since the dispersing composition of this invention has a high dye adsorption rate, it is easy to obtain high heat resistance.

It is thought that this cause is due to the dye concentration Ci at the time of preparation of the dispersion composition in the present invention being higher than the dye concentration Cf in the final dispersion composition. That is, it is thought that adsorption to a pigment is easy to occur by inject | pouring dye at a higher concentration (for example, dye input in the solid state at the time of pigment refinement as described in Example 1).

As shown in the comparative example, even if the dye is low in concentration (Comparative Example 1) even when charged in the dispersing step, and in the case of simply stirring and mixing after the dispersing step (Comparative Example 2), since the dispersion is not sufficient, the pigment Is not sufficiently disintegrated and the particle surface area is small (Comparative Example 3), the dye adsorption rate is low, and thus the heat resistance is also low.

In addition, surprisingly, the coloring photosensitive compositions 1-24 of this invention had the outstanding contrast compared with the coloring photosensitive compositions A-C of a comparative example. Although this reason is not fully clear, it is considered that the dye adsorb | sucked to the pigment surface and since the amount of glass dye in a dispersion composition is small, aggregation of dye in the coloring layer formation process is suppressed. It is presumed that contrast is improved because particles in the colored layer which cause light scattering are reduced by suppressing aggregation of the dye.

[Example 25]

<Production of Liquid Crystal Display Device>

The color filter was produced by the following method, the liquid crystal display device LCD-B1-LCD-B14 using this was produced, and the display characteristic was evaluated.

&Lt; Preparation of red colored photosensitive composition R >

The following red pigment dispersion composition was mixed and stirred at a rotational speed of 3,000 r.p.m. for 3 hours using a homogenizer. The mixed solution thus obtained was further subjected to a dispersion treatment for 12 hours with a bead disperser dispermat (manufactured by GETZMANN) using 0.3 mm φ zirconia beads, and furthermore, a high pressure disperser NANO-3000-10 with a decompression mechanism thereafter. Dispersion treatment was performed using BEE Co., Ltd. as a flow rate of 500 g / min under a pressure of 2000 kg / cm 3. This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

[Red Pigment Dispersion Composition]

C.I. Pigment Red 254 Part 75

C.I. Pigment Red 17 750

Benzyl methacrylate / methacrylic acid copolymer 70 parts

(Copolymerization Composition Ratio 70/30, Weight Average Molecular Weight 30000, Acid Value 40)

800 parts of propylene glycol monomethyl ether acetate

The component of the following composition was further added to the obtained pigment dispersion, and the red coloring photosensitive composition R was produced.

[Red Colored Photosensitive Composition R Composition]

100 parts of the red pigment dispersion

12 parts of a propylene glycol monomethyl ether acetate solution (50% solids) of a benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (Mw: 30,000)

Polymerizable compound 1: Nippon Kayaku Co., Ltd., KAYARAD DPHA 12.1 parts

Photoinitiator: 3.1 parts of 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer)

Deep dye: 4.2 parts of 4,4'-bis (diethylamino) benzophenone

Hydrogen donor compound: 2.1 parts of 2-mercaptobenzothiazole

Polymerization inhibitor: 0.001 part of p-methoxyphenol

0.5 part of fluorine-based surfactant (trade name: manufactured by Megafac R08 DIC Co., Ltd.)

Propylene glycol monomethyl ether acetate 60 parts

<Preparation of green colored photosensitive composition G>

In the preparation of the red colored photosensitive composition R, C.I. Instead of Pigment Red 254, C.I. Pigment Green 58, 103 parts, C.I. Instead of Pigment Red 177, C.I. A green colored photosensitive composition G was produced in the same manner except that 19 parts of Pigment Yellow 150 were used.

<Preparation of black coloring photosensitive composition K>

It changed to the pigment dispersion composition of the following composition, and carried out dispersion processing similarly to preparation of a red pigment dispersion, and produced the black pigment dispersion.

[Black Pigment Dispersion Composition]

Carbon black: Product name: Nipex35, Degusa Japan Co., Ltd. 13.1 part

Polymer: 6.7 parts of benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer (molecular weight: 370,000)

Propylene glycol monomethyl ether acetate 79.1 parts

0.65 parts of a dispersant (following compound)

The black coloring photosensitive composition K was composed of the following compositions using the obtained black pigment dispersion composition.

[Black coloring photosensitive composition K composition]

25 parts of the black pigment dispersion

8.5 parts of propylene glycol monomethyl ether acetate

53 parts methyl methyl ketone

Polymer: 9.1 parts of a mixture of 27 parts of benzyl methacrylate / methacrylic acid = 78/22 mole ratio random copolymer, molecular weight 3.8 million) and 73 parts of propylene glycol monomethyl ether acetate

Polymerization inhibitor: 0.002 parts of hydroquinone monomethyl ether

Polymerizable compound: 12 parts of KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.

Polymerization initiator: 0.16 parts of 2,4-bis (trichloroethyl) -6- [4 '(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine

0.042 parts of a 30% solution of methyl ethyl ketone of the surfactant (following compound)

&Lt; Fabrication of color filter &

&Lt; Formation of black matrix &

The alkali free glass substrate was wash | cleaned with the UV washing | cleaning apparatus, and then brush-cleaning using a washing | cleaning agent, and also ultrasonic cleaning with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state, and the substrate was cooled and temperature-controlled to 23 ° C.

The said black coloring photosensitive resin composition K was apply | coated with the coater for glass substrates (FAS Asia company make, brand name: MH-1600) which has a slit-shaped nozzle on the said board | substrate. Subsequently, VCD [vacuum drying device; Tokyo Okago Co., Ltd.] was dried for 30 seconds to remove the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a black photosensitive composition layer having a film thickness of 2.4 μm.

The distance between the exposure mask surface and the photosensitive resin layer in the state in which the substrate and the mask (quartz exposure mask having an image pattern) is vertically set by a proximity type exposure machine (manufactured by Hitachi Hi-Tech Denshi Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. It set to 200 micrometers and pattern-exposed at the exposure amount 300mJ / cm <2>.

Subsequently, pure water is sprayed with a shower nozzle, and the surface of the black photosensitive composition layer is uniformly wetted, followed by KOH-based developer (KOH, containing a nonionic surfactant, trade name: CDK-1, manufactured by Fuji Film Electronics Materials). The shower development was carried out at 80 ° C for 80 seconds at a flat nozzle pressure of 0.04 MPa to obtain a patterned image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure cleaning nozzle to remove residue. Finally, heat treatment was performed at 220 ° C. for 30 minutes to form a black matrix.

<Formation of RGB Pixel>

On the glass substrate on which the black matrix was formed, red colored photosensitive composition R, green colored photosensitive composition G, and the blue photosensitive composition prepared in Example 1 were laminated and patterned in the same manner as in the case of forming the black matrix, respectively, to obtain an RGB tricolor pixel. A color filter was obtained. At this time, the coloring part film thickness of each RGB color was 1.6 micrometers.

&Lt; Formation of ITO electrode &

The glass substrate in which the color filter was formed was put into the sputter apparatus, the ITO of 1300 micrometers thick was vacuum-deposited at 100 degreeC, and it annealed at 240 degreeC for 90 minutes, and ITO was crystallized and the ITO transparent electrode was formed.

<Formation of Spacer>

The spacer was formed on the above-mentioned ITO transparent electrode by the method similar to the spacer formation method of [Example 1] of Unexamined-Japanese-Patent No. 2004-240335.

&Lt; Formation of Liquid Crystal Alignment Control Projections >

The liquid crystal alignment control protrusion was formed on the ITO transparent electrode in which the said spacer was formed using the following coating liquid for positive photosensitive resin layers.

However, the following methods were used for the exposure, development, and baking steps.

Proximity exposure machine (manufactured by Hitachi Hi-Tech Denshi Engineering Co., Ltd.) is placed so that a predetermined photomask is at a distance of 100 µm from the surface of the photosensitive resin layer. Miti exposure.

Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed while spraying onto the substrate at 33 ° C. for 30 seconds with a shower developing device. In this way, the unnecessary part (exposed part) of the photosensitive resin layer was image-removed, and the board | substrate for liquid crystal display devices with which the processus | protrusion for liquid crystal orientation control which consists of the photosensitive resin layer patterned in the desired shape on the color filter side board | substrate was obtained.

Subsequently, the liquid crystal aligning control projection was formed on the substrate for liquid crystal display device by baking the liquid crystal display device substrate having the liquid crystal aligning control projection formed at 230 ° C. for 30 minutes.

[Prescription of Coating Liquid for Positive Photosensitive Resin Layer]

53.0 parts of positive resist liquid (FH-2413F manufactured by Fujifilm Electronics Material Co., Ltd.)

Methyl ethyl ketone 46.5 parts

Megapack F-780F (manufactured by DIC Corporation) 0.05 parts

<Production of Liquid Crystal Display Device>

The alignment film which consists of polyimide was further formed on the board | substrate for liquid crystal display devices obtained above. Subsequently, the epoxy resin sealant was printed at a position corresponding to the outer frame of the black matrix so as to surround the pixel group of the color filter, and the liquid crystal for MVA mode was dropped and bonded to the counter substrate. Was heat treated to cure the sealant.

Thus, polarizing plate HLC2-2518 made from Sanritsu Co., Ltd. was stuck to both surfaces of the obtained liquid crystal cell. Subsequently, as a light source, the LED light source (LCD television made by Sony, the backlight light source of KDL-40ZX1) was arrange | positioned at the side used as the back surface of the liquid crystal cell in which the said polarizing plate was provided, and it was set as the liquid crystal display device (LCD).

The liquid crystal display device produced as mentioned above had high contrast and brightness | luminance, and was suitable as a display device. In addition, although evaluation was performed in the MVA mode liquid crystal display device in this embodiment, good image quality can be obtained similarly by using the coloring effect composition of the present invention for the color filter of the liquid crystal display device or organic EL display of another mode. I think.

Claims (13)

(A) a blue pigment, (B) a dye having a parent skeleton different from the blue pigment, and (C) a polymerizable compound, wherein at least 15% by mass of the (B) dye is a It is adsorbed on the surface, The coloring photosensitive composition characterized by the above-mentioned. The method of claim 1,
The coloring photosensitive composition characterized by including the dispersion composition obtained by disperse | distributing the said (A) blue pigment and said (B) dye in situ. 3. The method of claim 2,
Said dispersion composition is a dispersion composition which satisfies the relationship of Ci> Cf when the density | concentration of the said (B) dye in the dispersion composition at the beginning of dispersion is Ci, and the density | concentration of the said (B) dye in the dispersion composition after completion | finish of dispersion is Cf. The coloring photosensitive composition characterized by the above-mentioned. The method of claim 1,
The dye (B) is a colored photosensitive composition, characterized in that the structure represented by the following general formula (I) is a metal complex compound disposed on a metal atom or a metal compound.

[In General Formula (I), R <^1> , R <^2> , R <^3> , R <^4> , R <^5> , and R <^6> respectively independently represent a hydrogen atom or a monovalent substituent, and R <^7> represents a hydrogen atom, a halogen atom, and an alkyl group. , Aryl group, or heterocyclic group] The method of claim 1,
After premixing the said (A) blue pigment and said (B) dye, the coloring photosensitive composition characterized by including the dispersion composition obtained by disperse | distributing the obtained color material mixture. The method of claim 1,
(D) a photopolymerization initiator. The method of claim 1,
(E) an alkali-soluble binder. A color filter produced by using the colored photosensitive composition according to any one of claims 1 to 7. A process for producing a colored photosensitive layer, comprising the steps of: forming a colored layer by providing the colored photosensitive composition according to any one of claims 1 to 7 on a support;
An exposure step of exposing the formed colored layer in a pattern shape;
It has a developing process of developing the colored layer after exposure and forming a coloring pattern, The manufacturing method of the color filter characterized by the above-mentioned. A display device comprising the color filter according to claim 8. A display device comprising the color filter obtained by the method for producing a color filter according to claim 9. (A) A blue pigment and (B) Disperse dye which has a parent skeleton different from the said blue pigment, a dispersion composition is prepared, and the coloring photosensitive composition is prepared using the said dispersion composition, The manufacture of the coloring photosensitive composition characterized by the above-mentioned. Way. (A) A blue pigment and (B) The dye which has a parent skeleton different from the said blue pigment is mixed, the color material composition is prepared, the said color material composition is disperse | distributed, the dispersion composition is prepared, and the coloring photosensitive composition is used using the said dispersion composition. The manufacturing method of the coloring photosensitive composition characterized by the above-mentioned.