TW201339755A - Colored photosensitive composition and production method thereof, color filter and production method thereof, and display device - Google Patents

Abstract

A colored photosensitive composition is provided. The colored photosensitive composition can form a colored layer which has good heat resistance, high luminance, and high contrast, when the colored layer is formed on a color filter or the like. The colored photosensitive composition includes (A) blue pigment, (B) dye which has different main skeleton from the blue pigment, and (C) polymerizable compound, and adsorption rate of the (B) dye to the surface of the (A) blue pigment is more than 15% by weight of the (B) dye.

Description

Coloring photosensitive composition, color filter, manufacturing method thereof, and display device

The present invention relates to a coloring photosensitive composition, a color filter, a method of manufacturing the same, and a display device.

Preparation of color sensitization for producing a color filter used in a liquid crystal display device or a solid-state imaging device (charge-coupled device (CCD), complementary metal-oxide semiconductor (CMOS), etc.) One of the methods of the sexual composition is known as a pigment dispersion method.

This pigment dispersion method is a method of producing a color filter by photolithography using a colored photosensitive composition obtained by dispersing a pigment in various photosensitive compositions. Since this method is patterned by the photolithography method, it is considered to be a method suitable for producing a color filter having high positional accuracy, large screen, and high definition. When a color filter is produced by a pigment dispersion method, a colored photosensitive composition is applied by a spin coater or a roll coater to form a coating film, and then the coating film is applied. The film is exposed and developed to form a colored pattern, which is repeated for each color, thereby obtaining a color filter. For the coloring photosensitive composition, for example, a blue coloring photosensitive composition for a color filter containing a phthalocyanine pigment is known (for example, refer to Japanese Patent No. 3,875,451).

In recent years, the performance requirements for color filters have become stricter, with particular emphasis on hue and brightness.

In response to such a situation, a technique of using a dye instead of a pigment has been proposed (for example, refer to Japanese Patent No. 3,837, 751, Japanese Patent Laid-Open No. 2008-292970, and Japanese Patent Laid-Open No. 2009-86375). However, it is known that a dye is generally inferior in heat resistance to a pigment, and further improved in order to fully exhibit the performance of the dye.

Therefore, a technique of using a dye together with a pigment has also been developed. For example, a water-based inkjet recording ink using a dye-adsorbed pigment is proposed (for example, Japanese Patent Laid-Open No. Hei 9-151344, Japanese Patent No. 4,170, 053), but it is not a technique capable of using a color filter. Therefore, further technical development is expected. Further, it has also been proposed to disperse a pigment by using a polymer dispersant to form a dispersion composition containing a dye which is not adsorbed on the surface of the pigment, and to provide a coloring photosensitive composition using the dispersion composition. (For example, refer to Japanese Laid-Open Patent Publication No. 2011-178865.)

Further, as a method of preparing a colored photosensitive composition using a pigment and a dye, a method of directly mixing a powder dye in a pigment dispersion liquid in which a pigment is dispersed is considered. law. In this method, when the solid content concentration in the composition is high or the mass ratio of the dye to the pigment is large, when the dye of the powder is directly added to the pigment dispersion liquid, there is a tendency that after the addition In the process of dissolving the dye in the solvent in the stirring and dissolving step, the dispersion state of the pigment changes, and the dispersibility and dispersion stability of the pigment are deteriorated.

Further, in this method, it is also required that the dissolution of the dye as a powder takes a long time, or the dye is not completely dissolved, or the dye is difficult to uniformly mix. Further, there is a concern that it is difficult to confirm the dissolution of the dye, and there are also obstacles in terms of production.

The colored photosensitive composition obtained by the above methods cannot sufficiently respond to the demand for a color filter having high heat resistance and capable of displaying high-quality images, and further improvement is desired.

The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a coloring photosensitive composition which can form a coloring layer which is excellent in heat resistance, high in brightness, and high in contrast when a coloring layer such as a color filter is formed.

Further, an object of the present invention is to provide a color filter which is formed by using the above-described colored photosensitive composition and which can display an image having high luminance and high contrast, a method for producing the same, and a displayable good image including the color filter. Quality display device.

The above object of the present invention is achieved by the following method.

<1> A colored photosensitive composition comprising: (A) a blue pigment, (B) a dye having a parent skeleton different from the above-described blue pigment, and (C) a polymerizable compound And 15% by mass or more of the above (B) dye is adsorbed on the surface of the above (A) blue pigment.

(2) The colored photosensitive composition according to <1>, which comprises a dispersion composition obtained by dispersing the (A) blue pigment and the (B) dye in the same system.

(3) The colored photosensitive composition according to <1> or <2>, wherein the dispersion composition is such that the concentration of the dye (B) in the dispersion composition at the initial stage of dispersion is Ci, and is dispersed. When the concentration of the dye (B) in the dispersion composition after completion is Cf, the dispersion composition satisfying the relationship of Ci>Cf is obtained.

The colored photosensitive composition according to any one of <1> to <3> wherein the (B) dye is a structure represented by the following formula (I) and is located on a metal atom or a metal compound. Metal complex compound:

In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, or an aromatic group. A group or a heterocyclic group.

The colored photosensitive composition according to any one of <1> to <4>, wherein the obtained colored material is obtained by premixing the (A) blue pigment and the (B) dye described above. The dispersion composition obtained by dispersing the mixture.

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

The colored photosensitive composition according to any one of <1> to <6> which further contains (E) an alkali-soluble binder.

<8> A color filter produced by using the coloring photosensitive composition according to any one of <1> to <7>.

<9> A method of producing a color filter, comprising: a colored layer forming step, wherein the colored photosensitive composition according to any one of <1> to <7> is applied onto a support to form a colored layer And an exposing step of exposing the formed coloring layer to a pattern pattern; and developing a step of developing the exposed coloring layer to form a colored pattern.

<10> A display device comprising the color filter according to <8> or a color filter obtained by the manufacturing method according to <9>.

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

<12> A method for producing a colored photosensitive composition, wherein the (A) blue pigment and the (B) dye are mixed to prepare a colored material composition, The colored material composition is dispersed to prepare a dispersion composition, and then the above-mentioned dispersion composition is used to prepare a colored photosensitive composition.

In the present invention, a blue pigment and a dye (having a mother skeleton different from the pigment) are used as a colorant to adsorb a part of the dye on the surface of the blue pigment, whereby it is presumed that the surface of the blue pigment is coated with the dye molecules. Since the dye is fixed to the surface of the pigment by being adsorbed on the pigment, the molecular motion of the dye is suppressed, and it is considered that the decomposition of the dye is suppressed even by heating, and the coloring formed by using the colored photosensitive composition of the present invention is considered to be colored. The layer suppresses discoloration even by heating. On the other hand, since the blue pigment is coated with the dye, even if the blue pigment forms fine particles by dispersion or the like, the coated dye functions as a protective colloid, and the dispersed state of the pigment is stably maintained. It is presumed that the dispersion stability of the blue pigment is improved, and the contrast and the like are improved.

Only by mixing a dye (dye powder or a dye solution dissolved in an organic solvent) in the pigment dispersion, usually the dye is not adsorbed on the pigment or even adsorbed, the adsorption rate is small. On the other hand, coloring sensitivity is prepared by using a dispersion composition in which a blue pigment and a dye are directly dispersed, or a mixture of colored materials containing a blue pigment and a dye in advance, and using a dispersion composition in which the mixture of the colored materials is dispersed. In the composition, the colored photosensitive composition of the present invention is obtained. Since the coloring photosensitive composition has an increased adsorption rate of the dye on the surface of the pigment, it is presumed that the obtained colored layer has high heat resistance and a layer having high contrast is obtained.

According to the present invention, it is possible to provide a colored photosensitive composition, which is colored When a coloring layer such as a color filter is formed, the optical composition can form a coloring layer having good heat resistance, high brightness, and high contrast.

Further, according to the present invention, it is possible to provide a color filter which is produced by using the colored photosensitive composition and which can display an image having high luminance and high contrast, and a method of manufacturing the same, and a color filter which can display good image quality. Display device.

The coloring photosensitive composition of the present invention is characterized by comprising (A) a blue pigment, (B) a dye having a parent skeleton different from the blue pigment (hereinafter referred to as "specific dye" as appropriate), and (C) The polymerizable compound, and 15% by mass or more of the specific dye is adsorbed on the surface of the above (A) blue pigment.

Further, the specific dye in the coloring photosensitive composition has an adsorption rate on the surface of the blue pigment of 15% by mass or more, preferably 20% by mass or more based on the specific dye. The upper limit of the amount of adsorption is preferably as high as possible in the gist of the present invention. However, if the surface of the pigment is excessively coated with the dye, the adsorption of the dispersant may be inhibited. Therefore, it is actually 90% by mass or less.

In the present specification, "~" indicates a range equal to or greater than the lower limit value and equal to or less than the upper limit value. Further, in the expression of the group in the present specification, the unsubstituted and unsubstituted expressions are not described as including not only a group having no substituent but also a group having a substituent.

Further, in the present specification, "the total solidity of the coloring photosensitive composition" The "component" refers to the total of the remaining components from which the organic solvent is removed from the total components constituting the colored photosensitive composition.

Further, in the present invention, the adsorption rate of the dye on the surface of the pigment is defined as the dye adsorption rate, which is expressed in %, and the dye adsorption rate is dispersed by using an ultracentrifuge (manufactured by Hitachi Koki Co., Ltd.) at 50,000 rpm. The composition was subjected to centrifugation, and the supernatant containing the free component was collected, and the amount of the dye in the obtained supernatant was measured by high performance liquid chromatography (HPLC), and was obtained according to the following mathematical formula. In addition, the ultracentrifuge used in the above-mentioned centrifugation is set to CS150GX (manufactured by Hitachi Ltd.), the centrifugal capacity is 1 g, and the centrifugation time (may vary depending on the sample) is usually about 1 hour to 6 hours. .

<Coloring photosensitive composition>

Hereinafter, the essential components and optional components constituting the colored photosensitive composition of the present invention will be described.

The coloring photosensitive composition of the present invention contains (A) a blue pigment, (B) a specific dye, and (C) a polymerizable compound as essential components.

[(A) Blue Pigment]

The colored photosensitive composition of the present invention comprises (A) a blue pigment, the blue As the color pigment, any of a blue organic pigment and a blue inorganic pigment may be used, and a blue organic pigment is preferred.

The blue organic pigment is preferably, for example, CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66 79. A pigment having 79 Cl substituents changed to OH and 80, and among these pigments, CI Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, and 66 are preferred.

Further, as for the average primary particle diameter of the blue pigment, in consideration of the fact that the high specific transmittance is preferable, it is preferred to select a pigment having a small particle size and a small grain size as much as possible. In particular, if the operability is also considered, 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. When the average primary particle diameter of the blue pigment is within the above range, it is effective for forming a color filter having high transmittance, good color characteristics, and high contrast.

The average primary particle diameter is observed by a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and 100 particle sizes are measured in a portion where the particles are not aggregated, and the calculation is performed. The average of the measured particle sizes was obtained.

In the colored photosensitive composition of the present invention, an organic pigment or an inorganic pigment other than the blue pigment may be further used for coloring or the like as needed.

Examples of the pigment other than the blue pigment which can be additionally used include the following organic pigments. However, in the present invention, the pigment which can be additionally used is not limited to these pigments.

CI 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; CI 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, 1 99, 213, 214; CI 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; CI Pigment Green 7, 10, 36, 37, 58; CI Pigment Violet 1, 19, 23, 27, 32, 37, 42; CI Pigment Brown 25, 28; CI Pigment Black 1.

Among the pigments which can be preferably used, the following pigments can be exemplified.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; CI Pigment Orange 36, 71; CI Pigment Red 122, 150, 171, 175, 177, 209 224, 242, 254, 255, 264; CI Pigment Violet 19, 23, 32; CI Pigment Green 7, 36, 37, 58; CI Pigment Black 1.

Further, examples of the inorganic pigment include metal compounds such as a metal oxide and a metal salt, and specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. And a composite oxide of the above metals.

[(B) specific dye]

The colored photosensitive composition of the present invention contains a dye (=specific dye) having a parent skeleton different from the (A) blue pigment.

The parent skeleton refers to a structure having a structure of a dye and a characteristic of a hue, and examples thereof include a structure such as phthalocyanine, pyrromethene, and anthraquinone.

The specific dye is not particularly limited as long as it is a dye having a parent skeleton different from the blue pigment. From the viewpoint of chemical structure, a pyrrolethymidine system or a pyrazole azo system can be used. Anilino azo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol , pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine Pyrrolopyrazole azomethine), xanthene, phthalocyanine, benzopyran, indigo, etc. dyes.

For example, the pigments described in the following patent documents are disclosed in Japanese Patent Laid-Open Publication No. SHO-64-90403, Japanese Patent Application Laid-Open No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 8-146215, Japanese Patent Laid-Open No. Hei 11-343437, Japanese Patent Laid-Open No. Hei 8-62416, and Japanese Japanese Laid-Open Patent Publication No. 2002-14220, Japanese Patent Laid-Open Publication No. 2002-14221, Japanese Patent Laid-Open Publication No. 2002-14222 Japanese Patent Laid-Open No. Hei 8-73758, Japanese Patent Laid-Open No. Hei 8-179120, Japanese Patent Laid-Open No. Hei 8-151531, and the like.

(dipyrromethene metal complex compound)

Among the dyes, a dye which is suitable as a specific dye for the coloring photosensitive composition of the present invention may be a metal complex compound having a structure represented by the following formula (I) and which is bonded to a metal atom or a metal compound (hereinafter referred to as a suitable compound) It is a "dipyrromethene-based metal complex compound").

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

In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, or an aromatic group. A group or a heterocyclic group.

The monovalent substituent (hereinafter sometimes referred to as a substituent R) represents a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom), an alkyl group (preferably having a carbon number of 1 to 48, more preferably a carbon number of 1). a straight chain, a branched chain, or a cyclic alkyl group of 24, for example: methyl, Ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclo A pentyl group, a cyclohexyl group, a 1-norbornyl group, a 1-adamantyl group, an alkenyl group (preferably a carbon number of 2 to 48, more preferably an alkenyl group having 2 to 18 carbon atoms, for example, a vinyl group, an allylic group) a group, a 3-buten-1-yl group, an aryl group (preferably a carbon number of 6 to 48, more preferably an aryl group having a carbon number of 6 to 24, for example, a phenyl group, a naphthyl group) or a heterocyclic group (more Preferred are heterocyclic groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2- a benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, a benzotriazol-1-yl group, a decylalkyl group (preferably a decyl group having a carbon number of 3 to 38, more preferably a carbon number of 3 to 18, For example: trimethyl decyl, triethyl decyl, tributyl decyl, tert-butyl dimethyl decyl, third hexyl dimethyl decyl, hydroxy, cyano, nitro, alkoxy a base (preferably alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy ,third An oxy group, a dodecyloxy group, or a cycloalkoxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group, or an aryloxy group (preferably having a carbon number of 6 to 48, more preferably a carbon number) 6 to 24 aryloxy groups, for example, phenoxy group, 1-naphthyloxy group, heterocyclic oxy group (preferably a carbon number of 1 to 32, more preferably a carbon number of 1 to 18, for example, a heterocyclic oxy group, for example, : 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), decyloxy (preferably a decyloxy group having a carbon number of 1 to 32, more preferably a carbon number of 1 to 18) a group, for example, a trimethylsilyloxy group, a tert-butyldimethylsilyloxy group, a diphenylmethylphosphonyloxy group, a decyloxy group (preferably a carbon number of 2 to 48, more preferably a nonyloxy group having 2 to 24 carbon atoms, for example, an ethoxycarbonyl group, a p-pentyloxy group, a benzhydryloxy group, a dodecyloxy group, an alkoxycarbonyl group (preferably a carbon number 2) ~48, More preferably, it is an alkoxycarbonyloxy group having 2 to 24 carbon atoms, for example, an ethoxycarbonyloxy group, a third butoxycarbonyloxy group, and, if it is a cycloalkyloxycarbonyloxy group, for example: Cyclohexyloxycarbonyloxy), aryloxycarbonyloxy (preferably an aryloxycarbonyloxy group having a carbon number of 7 to 32, more preferably 7 to 24 carbon atoms, for example, a phenoxycarbonyloxy group) Aminomethyloxy (preferably a carbon number of 1 to 48, more preferably an aminomethyloxy group having a carbon number of 1 to 24, for example, N,N-dimethylaminemethyl methoxy, N-butyl Aminomethyl methoxy, N-phenylamine methyl methoxy, N-ethyl-N-phenylamine methyl methoxy, sulfonyloxy (preferably from 1 to 32, more preferably Aminosulfonyloxy group having 1 to 24 carbon atoms, for example, N,N-diethylamine sulfonyloxy group, N-propylamine sulfonyloxy group, alkylsulfonyloxy group (preferably carbon number) 1 to 38, more preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyl An oxy group (preferably an arylsulfonyloxy group having a carbon number of 6 to 32, more preferably a carbon number of 6 to 24, for example, a phenylsulfonyloxy group) or a mercapto group (preferably having a carbon number of 1 to 48). More preferably a thiol group with a carbon number of 1 to 24, for example: a base, an ethyl sulfonyl group, a pentylene group, a benzamidine group, a tetradecyl group, a cyclohexyl group, an alkoxycarbonyl group (preferably having a carbon number of 2 to 48, more preferably a carbon number of 2 to 24) Alkoxycarbonyl group, for example: methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl An aryloxycarbonyl group (preferably an aryloxycarbonyl group having a carbon number of 7 to 32, more preferably a carbon number of 7 to 24, for example, a phenoxycarbonyl group) or an amine formazan group (preferably having a carbon number of 1 to 2) 48. More preferably, it is an amine carbenyl group having a carbon number of 1 to 24, for example, an amine methyl sulfonyl group, an N,N-diethylamine methyl fluorenyl group, an N-ethyl-N-octylamine fluorenyl group, and a N group. , N-dibutylamine methyl sulfhydryl, N-propylamine methyl sulfhydryl, N-phenylamine methyl sulfhydryl, N-methyl N-phenylamine formazan Base, N,N-dicyclohexylaminecarbamyl), amine group (preferably having an alkyl group of 32 or less, more preferably a carbon number of 24 or less, for example, an amine group, a methylamino group, N, N a dibutylamino group, a tetradecylamino group, a 2-ethylhexylamino group, a cyclohexylamino group, an anilino group (preferably an anthranyl group having a carbon number of 6 to 32, more preferably 6 to 24). For example: anilino, N-methylanilino), heterocyclic amine (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18, for example, 4-pyridylamino group), carboxy Amidino group (preferably a carboguanamine group having a carbon number of 2 to 48, more preferably 2 to 24, for example, an acetamino group, a benzammonium group, a tetradecylguanidinyl group, a benzalkonium group , cyclohexylamine), urea group (preferably a carbazide having a carbon number of 1 to 32, more preferably a carbon number of 1 to 24, for example, urea group, N,N-dimethylureido group, N-benzene) a ureido group, preferably a quinone imine group having a carbon number of 36 or less, more preferably a carbon number of 24 or less, for example, N-butanediamine, N-phthalimin Amino), alkoxycarbonylamino (preferably alkoxycarbonylamino having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonylamino group, ethoxycarbonylamine) Base a butoxycarbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamino group, an aryloxycarbonylamino group (preferably having a carbon number of 7 to 32, more preferably a carbon number of 7 to 24) An aryloxycarbonylamino group, for example, a phenoxycarbonylamino group, a sulfonylamino group (preferably a sulfoniumamino group having a carbon number of 1 to 48, more preferably a carbon number of 1 to 24, for example, methylsulfonium) Amine, sulfonamide, benzenesulfonylamino, hexadecanoylamino, cyclohexylsulfonylamino), aminesulfonylamino (preferably carbon number 1 to 48, more preferably carbon) Aminosulfonylamino group of 1 to 24, for example, N, N-dipropylaminesulfonylamino, N-ethyl-N-dodecylamaminesulfonylamino), azo (preferably an azo group having a carbon number of 1 to 32, more preferably a carbon number of 1 to 24, for example, a phenylazo group or a 3-pyrazolylazo group), An alkylthio group (preferably an alkylthio group having a carbon number of 1 to 48, more preferably a carbon number of 1 to 24, for example, a methylthio group, an ethylthio group, an octylthio group or a cyclohexylthio group) or an arylthio group ( It is preferably an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, a phenylthio group or a heterocyclic thio group (preferably having a carbon number of 1 to 32, more preferably a carbon number of 1 to 2). a heterocyclic thio group of 18, for example, a 2-benzothiazolylthio group, a 2-pyridylthio group, a 1-phenyltetrazolylthio group, an alkylsulfinyl group (preferably a carbon number of 1~) 32. More preferably, it is an alkylsulfinylene group having 1 to 24 carbon atoms, for example, dodecylsulfinyl group, and an arylsulfinylene group (preferably having a carbon number of 6 to 32, more preferably a carbon number) 6 to 24 arylsulfinyl groups, for example, phenylsulfinyl), alkylsulfonyl (preferably a carbon number of 1 to 48, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms) For example: methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl , octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl (preferably an arylsulfonyl group having a carbon number of 6 to 48, more preferably a carbon number of 6 to 24, for example, phenylsulfonate Base, 1-naphthylsulfonyl), A sulfonyl group (preferably a sulfonyl group having a carbon number of 32 or less, more preferably a carbon number of 24 or less, for example, an amine sulfonyl group, an N,N-dipropylamine sulfonyl group, or an N-ethyl-N group - dodecylamine sulfonyl, N-ethyl-N-phenylamine sulfonyl, N-cyclohexylamine sulfonyl), sulfo, phosphonyl (preferably carbon number 1) More preferably, it is a phosphonium group having a carbon number of 1 to 24, for example, a phenoxyphosphonium group, an octyloxyphosphonium group, a phenylphosphonium group, or a phosphinoylamino group. It is preferably a phosphinium group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, diethoxyphosphinylamino group or dioctyloxyphosphinylamino group.

In the case where the above monovalent group is a group which can be further substituted, Any of the groups described above is further substituted. Further, in the case of having two or more substituents, the substituents may be the same or different.

In the formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ may be independently bonded to each other to form a ring of 5 members, 6 members, or 7 members. . Further, the ring formed has a saturated ring or an unsaturated ring. Examples of the saturated ring or the unsaturated ring of the 5-member, the 6-membered member, or the 7-membered member 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, and a pyrrole group. The pyridine ring, the piperidine ring, the cyclopentene ring, the cyclohexene ring, the benzene ring, the pyridine ring, the pyrazine ring, and the pyridazine ring are preferably a benzene ring or a pyridine ring.

Further, in the case where the formed ring of 5 members, 6 members, and 7 members is a group which may be further substituted, it may be substituted by any of the above substituents R, and may be substituted with two or more substituents. Hereinafter, the substituents may be the same or different.

Further, in the case where R ⁷ in the formula (I) is a halogen atom, an alkyl group, an aryl group or a heterocyclic group, a preferred range of the groups is as a halogen atom or an alkyl group as the above R ¹ to R ⁶ The preferred ranges of the aryl group, the aryl group or the heterocyclic group are the same.

In the formula (I), the above R ¹ and R ^{6 are} preferably an alkylamino group, an arylamine group, a carboxylammonium group, a ureido group, a quinone imine group or an alkoxycarbonylamino group in the above group. , sulfonamide, more preferably carboguanamine, ureido, alkoxycarbonylamino, sulfonylamino, especially preferably carboguanamine, ureido, alkoxycarbonylamino, sulfonamide The base is particularly preferably a carboxy guanamine group or a ureido group.

In the formula (I), the above R ² and R ^{5 are} preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an amine methyl sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group or a nitrile group in the above group. , 醯imino, amidyl sulfonyl sulfhydryl, more preferably alkoxycarbonyl, aryloxycarbonyl, amine carbaryl, alkylsulfonyl, nitrile, quinone, amidyl Sulfhydryl group, particularly preferably alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, nitrile, oxime imido, amine mercaptosulfonyl, particularly preferably alkoxycarbonyl, aryloxycarbonyl Aminomethyl thiol.

In the formula (I), the above R ³ and R ^{4 are} preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic ring in the above group. Further, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group is preferred.

In the formula (I), in the case where R ³ and R ⁴ represent an alkyl group, the alkyl group is preferably a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. More specifically, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, The cyclohexyl group and the benzyl group are more preferably a branched chain having 1 to 12 carbon atoms or a cyclic substituted or unsubstituted alkyl group, and more specifically, for example, an isopropyl group or a cyclopropyl group. Isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, especially preferably a secondary or tertiary substituted or unsubstituted alkyl group having from 1 to 12 carbon atoms, more specifically, for example Examples thereof include an isopropyl group, a cyclopropyl group, an isobutyl group, a tert-butyl group, a cyclobutyl group, and a cyclohexyl group.

In the general formula (I), in the case where R ³ and R ⁴ represent an aryl group, the aryl group is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, more preferably It is a substituted or unsubstituted phenyl group.

In the case where R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group is preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, or substituted. Or unsubstituted 3-pyridyl, substituted or unsubstituted 2-pyridyl, substituted or unsubstituted 2-furyl, substituted or unsubstituted 2-pyrimidinyl, substituted or not Substituted 2-benzothiazolyl, substituted or unsubstituted 1-imidazolyl, substituted or unsubstituted 1-pyrazolyl, substituted or unsubstituted benzotriazol-1-yl More preferably, it may be exemplified by a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted 2-furyl group, substituted or unsubstituted. 2-pyrimidinyl, substituted or unsubstituted 1-pyridyl.

Next, a metal atom or a metal compound which forms a dipyrromethene-based metal complex compound will be described.

The metal or metal compound may be any of a metal atom or a metal compound which can form a complex compound, and includes a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., also includes AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , metal chloride such as GeCl ₂ , metal oxide such as TiO or VO, metal hydroxide such as Si(OH) ₂ .

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

A preferred embodiment of the dipyrromethene-based metal complex compound having a structure in which the compound represented by the above formula (I) is bonded to a metal atom or a metal compound is shown below. The following embodiments are exemplified: in the 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 decyl group, a hydroxy group, a cyano group or an alkoxy group. , aryloxy, heterocyclic oxy, fluorenyl, alkoxycarbonyl, aminecarbamyl, amine, anilino, heterocyclic amine, carboxamide, ureido, quinone, alkoxy Carbonylamino, aryloxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclothio, alkylsulfonyl, arylsulfonyl, or phosphinium Amine, R ² and R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, or a heteroepoxy group. Base, mercapto group, alkoxycarbonyl group, aryloxycarbonyl group, amine mercapto group, quinone imine group, alkoxycarbonylamino group, sulfonylamino group, azo group, alkylthio group, arylthio group, hetero An episulfide group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group, and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, Decyl, hydroxy, cyano Alkoxy, aryloxy, heterocyclooxy, decyl, alkoxycarbonyl, aminemethanyl, anilino, carboxy oxime, ureido, quinone, alkoxycarbonyl, sulfonate Amidino, azo, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, sulfonyl, or phosphinium, R ⁷ represents hydrogen The atom, the halogen atom, the alkyl group, the aryl group or the heterocyclic group, the metal atom or the metal compound is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B or VO.

A more preferred embodiment of the dipyrromethene-based metal complex compound is shown below. The following embodiments are exemplified: in the above 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 cyano group, a decyl group or an alkoxycarbonyl group. , Aminomethyl, Amino, Heterocyclic Amine, Carboxylammonium, Urea, Iminoimine, Alkoxycarbonylamino, Aryloxycarbonylamino, Sulfonylamino, Azo, Alkylsulfonyl, arylsulfonyl, or phosphiniumamino, R ² and R ⁵ each independently represent alkyl, alkenyl, aryl, heterocyclyl, cyano, nitro, fluorenyl An alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbenyl group, an oxime imido group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group, and R ³ and R ⁴ each independently represent a hydrogen atom. An alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group, an alkoxycarbonyl group, an amine carbaryl group, a carbamoylamino group, a ureido group, a quinone imine group, an alkoxycarbonylamino group, Sulfonyl, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, or aminesulfonyl, R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group Or a heterocyclic group, a metal atom or The metal compound is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO.

A preferred embodiment of the dipyrromethene-based metal complex compound in which the compound represented by the above formula (I) is bonded to a metal atom or a metal compound is a miscellaneous formula represented by the following formula (I-3) Compound.

General formula (I-3)

In the above 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 a heterocyclic ring. base. 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. 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, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or 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, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur An atom, or a carbon atom. X ⁵ represents a group which can bind to Ma, and a represents 0, 1, or 2. R ⁸ and Y ¹ may be combined to form a ring of 5 members, 6 members, or 7 members, and R ⁹ and Y ² may be combined with each other to form a ring of 5 members, 6 members, or 7 members.

General formula R (I-3) in ² ~ R ^5, and R ⁷ in the general formula (I) in R ² ~ R ^5, and by the same meaning as R ^7, preferred embodiments are also the same.

Ma in the general formula (I-3) represents a metal or a metal compound, and the above The metal atom or the metal compound in which the compound represented by the formula (I) is coordinated to a metal atom or a metal compound has the same meaning, and the preferred range thereof is also the same.

In the formula (I-3), R ⁸ and R ⁹ each independently represent 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, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12, for example, a vinyl group, an allyl group, a 3-buten-1-yl group) or an aryl group. (preferably, an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18, for example, a phenyl group or a naphthyl group) or a heterocyclic group (preferably having a carbon number of 1 to 24, more preferably 1 to 12) a cyclic group such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzo Triazol-1-yl), alkoxy (preferably alkoxy having 1 to 36 carbon atoms, more preferably 1 to 18, such as methoxy, ethoxy, propoxy, butoxy, Hexyloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy), aryloxy (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, for example: Phenoxy, naphthyloxy), alkylamino group ( Preferred are alkylamino groups having 1 to 36 carbon atoms, more preferably 1 to 18, such as methylamino, ethylamino, propylamino, butylamino, hexylamino, 2-ethyl Hexylamino, isopropylamino, tert-butylamino, trioctylamino, cyclohexylamino, N,N-diethylamino, N,N-dipropylamino, N , N-dibutylamino group, N-methyl-N-ethylamino group), arylamine group (preferably an arylamino group having a carbon number of 6 to 36, more preferably 6 to 18, for example: Phenylamino, naphthylamino, N,N-diphenylamino, N-ethyl-N-phenylamino), or heterocyclic amine (preferably from 1 to 24, more preferably It is a heterocyclic amino group of 1 to 12, for example, 2-aminopyrrolyl, 3-aminopyrazolyl, 2-aminopyridyl, 3-aminopyridyl).

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

In the formula (I-3), X ³ and X ⁴ each independently represent NRa, an oxygen atom or a sulfur atom. Ra represents 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, for example, methyl group, ethyl group, propyl group, or isopropyl group). , butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl (preferably An alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12, for example, a vinyl group, an allyl group, a 3-buten-1-yl group, or an aryl group (preferably having a carbon number of 6 to 36, more preferably An aryl group of 6 to 18, for example, a phenyl group, a naphthyl group, or a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, for example, 2-thienyl group, 4-pyridine) , 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), decyl (preferably) It is a fluorenyl group having 1 to 24 carbon atoms, more preferably 2 to 18, for example, an ethyl group, a pentylene group, a 2-ethylhexyl group, a benzamidine group, a cyclohexyl group, or an alkylsulfonyl group. (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably 1 to 18, for example, methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl) Arylsulfonyl group 6 to 24 carbon atoms, more preferably an aryl group having 6 to 18 Sulfonic group, for example: phenyl sulfonic acyl, sulfo acyl naphthyl group). Further, in the case where Ra is substitutable, it may be further substituted by a substituent, and in the case of being substituted by a plurality of substituents, the substituents may be the same or different.

X ³ and X ⁴ are each preferably an oxygen atom or a sulfur atom, and X ³ and X ⁴ are each preferably an oxygen atom.

In the general formula (I-3), Y ¹ and Y ² each independently represent NRb, a sulfur atom or a carbon atom, and Rb has the same meaning as Ra in the above X ³ .

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

In the formula (I-3), R ⁸ and Y ¹ may be bonded to each other to form a 5-membered ring together with R ⁸ , Y ¹ and a carbon atom (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, Tetrahydrothiophene, pyrrole, furan, thiophene, anthracene, benzofuran, benzothiophene), 6-membered ring (eg cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, Pentamethyl sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline, or a 7-membered ring (eg, cycloheptane, hexamethylene) Imine).

In the formula (I-3), R ⁹ and Y ² may be bonded to each other to form a ring of 5 members, 6 members, or 7 members together with R ⁹ , Y ² , and a carbon atom. The ring of the five members, the six members, and the seven members formed may be a ring in which one of the bonds formed by R ⁸ and Y ¹ and a carbon atom is changed to a double bond.

In the general formula (I-3), when the ring of 5 members, 6 members, and 7 members formed by combining R ⁸ and Y ¹ and R ⁹ and Y ^{2 is} a ring which can be further substituted, the above may be carried out. Substituents described in any of the substituents R may be substituted or substituted with two or more substituents, and the substituents may be the same or different.

In the formula (I-3), X ⁵ represents a group which can bind to Ma. X ⁵ represents, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, or a bromine atom), a hydroxyl group, and an aliphatic quinone imide (for example, butyl imidate, maleimide, pentane) The quinone imine, the diethylamine or the like is preferably a monovalent group of succinimide or maleimide, derived from an aromatic quinone or a heterocyclic quinone (for example). For example, phthalimide, naphthyl imine, 4-bromophthalimide, 4-methylphthalimide, 4-nitrophthalic acid oxime The imine, naphthyl quinone imine, tetrabromo phthalimide, etc., preferably include phthalimide, 4-bromophthalimide, 4-methyl phthalic acid. The monovalent group of dimethyl sulfoxide is derived from an aromatic carboxylic acid (for example, benzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 4 - chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxybenzoic acid, 4-tert-butylbenzoic acid, etc., preferably exemplified a monovalent group of formic acid, 4-methoxybenzoic acid, salicylic acid, etc. derived from an aliphatic carboxy group The acid (for example, formic acid, acetic acid, acrylic acid, methacrylic acid, acetic acid, propionic acid, lactic acid, pivalic acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, myristic acid, Palmitic acid, stearic acid, oleic acid, isostearic acid, 2-hexadecyl octadecanoic acid, 2-hexyl decanoic acid, cyclopentylic acid, cyclohexylcarboxylic acid, 5-northene-2-carboxylate The acid, 1-adamantanecarboxylic acid or the like is preferably a monovalent group derived from acetic acid, methacrylic acid, lactic acid, pivalic acid, 2-ethylhexanoic acid or stearic acid, derived from dithiouric acid. (For example, a monovalent group of dimethyldithiocarbamic acid, diethyldithiol formic acid, and dibenzyldithiolcarboxylic acid), which is derived from a sulfonamide (for example, benzenesulfonamide, 4) - chlorobenzenesulfonamide, 4-methoxybenzenesulfonamide, 4-methylbenzenesulfonamide, 2-methylbenzenesulfonamide, methanesulfonamide, preferably phenylsulfonamide, The monovalent group of metosulfamide is derived from hydroxamic acid (for example, acetohydroxamic acid, octanohydroxamic acid, benzohydroxamic acid) One-price base a ring compound (exemplified by: carbendazim, 1-benzyl-5-ethoxyethyl carbazide, 1-allyl carbendazim, 5,5-diphenylethylene carbazide, 5, 5-dimethyl-2,4-oxazolidinedione, barbituric acid, imidazole, pyrazole, 4,5-dicyanoimidazole, 4,5-dimethylimidazole, benzo Imidazole, diethyl 1H-imidazole-4,5-dicarboxylate, etc., preferably 1-benzyl-5-ethoxybenzamide, 5,5-dimethyl-2,4-oxo A monovalent group of oxazolidinedione, 4,5-dicyanoimidazole, 1H-imidazole-4,5-dicarboxylate.

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

Preferred embodiments of the compound represented by the formula (I-3) are shown below. That is, the following embodiments: R ² to R ⁵ , R ⁷ , and Ma are each a preferred embodiment comprising a complex of a compound represented by the formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are respectively Independently, NRa (Ra is a hydrogen atom, an alkyl group, a heterocyclic group), or an oxygen atom, and 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 a group bonded via an oxygen atom or a nitrogen atom, and R ⁸ and R ⁹ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, and R ⁸ and Y ¹ Combining with each other to form a 5-member or 6-membered ring, R ⁹ and Y ² are combined to form a 5-membered, 6-membered ring, and a represents 0 or 1.

A more preferred embodiment of the compound represented by the formula (I-3) is shown below. That is, the following embodiments: R ² to R ⁵ , R ⁷ and Ma are each a preferred embodiment comprising a complex of a compound represented by the formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are oxygen. An atom, Y ¹ is NH, Y ² is a nitrogen atom, X ⁵ is a group bonded via an oxygen atom or a nitrogen atom, and R ⁸ and R ⁹ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group. A group or an alkylamine group, R ⁸ and Y ¹ are bonded to each other to form a 5-membered or 6-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered or 6-membered ring, and a represents 0 or 1.

Specific examples of the dipyrromethene-based metal complex compound in which the compound represented by the above formula (I) used in the present invention is bonded to a metal atom or a metal compound are shown below. However, the present invention is not limited to these specific examples.

In the exemplary compounds of the dipyrromethene-based metal complex compound in which the compound represented by the formula (I) is bonded to a metal atom or a metal compound, the exemplified compound (1) to the exemplified compound (39) are also An exemplified compound of the formula (I-3).

In addition, examples of the dipyrromethene-based metal complex compound in which the compound represented by the formula (I) is bonded to a metal atom or a metal compound, in addition to the above-exemplified compounds, may be mentioned. Exemplary compounds (Ia-3) to exemplified compounds (Ia-83), exemplified compounds (IIa-1) to exemplified compounds (IIa-20), and exemplified compounds (I-1) to exemplified compounds (I) -36), exemplified compound (II-1) to exemplified compound (II-11), and exemplified compound (III-1) to exemplified compound (III-103), and exemplified compound (I-1) described in Japanese Patent No. 3324279 )~Illustrated Compound (I-35), Japan The exemplified compound (I-1) to the exemplified compound (I-13) described in Japanese Patent No. 3279035, and the exemplified compound (2-1) to the exemplified compound (2-32) and the exemplified compound (Japanese Patent Laid-Open No. Hei 11-256057) 3-1) to exemplified compound (3-32), exemplified compound (4-1) to exemplified compound (4-26), and exemplified compound (5-1) to exemplified compound (5-26), Japanese Patent Laid-Open Illustrative compound (I-1) to exemplified compound (I-6) and exemplified compound (VII-1) to exemplified compound (VII-8) described in JP-A-H11-352686, 1-1) to exemplified compounds (1-45), exemplified compounds (1-1) to exemplified compounds (1-50) described in JP-A-2000-19729, and exemplified compounds described in JP-A-H11-352685 (1-1) to exemplified compounds (1-45) and the like.

[dispersed composition]

The colored photosensitive composition of the present invention preferably contains a dispersion composition. As a method of obtaining the colored photosensitive composition of the present invention, a preferred dispersion composition will be described.

In the colored photosensitive composition of the present invention, (B) 15% by mass or more of the specific dye is adsorbed on the surface of the (A) blue pigment. When the adsorption ratio of the (B) specific dye to the surface of the (A) blue pigment is in the above range, the coloring layer obtained by using the colored photosensitive composition of the present invention has good heat resistance and can exhibit high contrast. The method of adsorbing a specific dye on the blue pigment may be any method, and it is preferred to prepare a dispersion composition containing a blue pigment and a specific dye in advance.

(colored material composition)

In addition, in order to obtain the dispersed composition, it is preferred to use blue pigment and special The dye is premixed to form a colored material composition, which is then subjected to dispersion treatment in the same system to prepare a dispersion composition. In other words, it is preferred to prepare a slurry (colored material composition) obtained by mixing a pigment and a dye, if necessary, a solvent or a dispersant, an additive, an abrasive, or the like, and the slurry is collectively introduced into a dispersion system. Disperse treatment. Therefore, in the present invention, before the salt milling described later or before the dispersion treatment by the disperser, the multistage dispersion treatment is further performed by the disperser, and before each of the stages, either In the case where the slurry in which the dye is previously mixed is subjected to dispersion treatment, it is referred to as pre-mixing. In addition, the above-mentioned "in the same system" means that the dispersion treatment is performed in the same dispersion batch in the same dispersion apparatus.

The pre-mixing method may be selected from a plurality of methods, and the blue pigment may be mixed with a specific dye of a solid using the organic solvent (F) described later, or a blue pigment may be dissolved in a specific solvent which is dissolved in an organic solvent (F) described later. The dye solution is mixed.

The mixing method may be a usual method using a stirrer or the like, or a two-roll mill, a three-roll mill, a ball mill, a trummel mill, a disperser, a kneader, a two-way kneader (ko-kneader) ), a homogenizer, a blender, a uniaxial or biaxial extruder, etc., and a method of kneading while imparting a strong shearing force, and it is preferable to carry out kneading from the viewpoint of increasing the adsorption rate of the dye. Methods.

(salt grinding)

The pigment usually aggregates, and in order to preliminarily break before dispersion, it is preferred to carry out a salt polishing treatment to be described later as a pigment refining treatment. At this time, as a method of mixing the dye and the pigment, a special solution may be added in the form of a solution or a solid during the salt grinding treatment. The dye is used to prepare the above colored material composition.

The refinement of the pigment is achieved by the following steps (salt grinding): preparing a high-viscosity liquid composition together with a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, and applying a stress using a wet pulverizing device or the like grinding. At this time, a specific dye may be added together with the pigment in a solution or a solid as needed to obtain a colored material mixture.

The water-soluble organic solvent used in the micronization step of the pigment may, for example, be methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol or diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, and the like.

In addition, other solvents having low water solubility or no water solubility can be used, for example, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, acetic acid Ester, isopropyl acetate, butyl acetate, hexane, heptane, octane, decane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbon, acetone, A Base ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl hydrazine, N-methyl pyrrolidone, and the like.

The solvent used in the step of miniaturizing the pigment may be used alone or in combination of two or more kinds as needed.

The water-soluble inorganic salt used in the step of refining the pigment may, for example, be sodium chloride, potassium chloride, calcium chloride, barium chloride or sodium sulfate.

The water-soluble inorganic salt used in the refining step is used in an amount of from 1 to 50 times by mass of the pigment, and the refining step in which the amount of the water-soluble inorganic salt used is large has The grinding effect, but in terms of productivity, the better amount is 1 mass to 10 mass times of the pigment. Further, it is preferred to use an inorganic salt having a water content of 1% or less.

The amount of the water-soluble organic solvent used in the miniaturization step is in the range of 50 parts by mass to 300 parts by mass, preferably 100 parts by mass to 200 parts by mass, based on 100 parts by mass of the pigment.

The operating conditions of the wet pulverizing apparatus in the step of miniaturizing the pigment are not particularly limited, and in order to effectively grind using the pulverizing medium, the operating condition in the case where the apparatus is a kneading machine is: the rotation speed of the blade in the apparatus is higher It is preferably 10 rpm to 200 rpm, and the rotation of the biaxial shaft is larger than that of the relatively large one. The running time is preferably from 1 hour to 8 hours in combination with the dry pulverization time, and the internal temperature of the device is preferably from 50 ° C to 150 ° C. Further, the water-soluble inorganic salt as the pulverization medium has a pulverized particle size of 5 μm to 50 μm, and the distribution of the particle diameter is sharp, and is preferably spherical.

The composition ratio of the blue pigment to the specific dye in the colored material composition is preferably 1:1 to 10:1, and particularly preferably 2:1 to 10:1. By setting it as the range, the adsorption rate of the specific dye on the surface of the blue pigment can be made 15% by mass or more of the specific dye, and the effect of the present invention can be exhibited.

Further, the total of the pigment and the dye in the colored material composition is preferably from 10% by mass to 60% by mass based on the total solid content in the colored material composition.

(Manufacturing method of dispersed composition)

The dispersion composition is obtained by dispersing a blue pigment and a specific dye using an organic solvent (F) described later. In this case, it is preferred to use the above-described colored material composition instead of the blue pigment and the specific dye.

Further, a dispersant, a pigment derivative, and other components described later may be added to the dispersion composition, and a pigment other than the blue pigment may be added.

The dispersion composition of the present invention can be obtained by adding or staging the above-mentioned respective components, using, for example, a vertical or horizontal sand grinder, a pin mill, a slit mill. A disperser such as a slit mill is microdispersed by using beads formed of glass having a particle diameter of 0.01 mm to 1 mm, zirconium oxide or the like.

When the blue pigment and the specific dye are dispersed without pre-mixing without passing through the colored material composition, it is preferred to put the dye into the dispersion device during the dispersion of the pigment, particularly preferably in the initial stage of dispersion. Invest. In this case, if a large amount of dye is added at once, it is easy to form agglomerates and it is not preferable, so it is preferable to introduce them slowly.

Further, when a specific dye is added to the dispersion device, a dye solution of a specific dye may be added. However, in terms of solubility and the like, it is preferably added in a solid state if possible. In the case of adding as a dye solution, it is also preferred that the dye concentration after the addition is as high as possible. The reason for this is that the higher the concentration of the dye in the system for dispersing the composition, the more the adsorption of the pigment is promoted, and as a result, the effect of the present invention (i.e., the heat resistance is improved) is more easily achieved. From this point of view, the addition of the dye is preferably carried out at the time of salt polishing or in the initial stage of dispersion, and in the case of using a multistage dispersion described later, it is preferred to carry out the initial stage of dispersion in the first stage.

As a method for preparing the dye solution, an organic solvent may be added to the dye to stir, but in terms of being easily dissolved, it is preferably an organic solvent being stirred. A method of introducing a powder dye into a dose. The method of inputting the dye can be used in a total amount, and can be input in stages.

As a method of dissolving the dye, a solution containing the dye and the organic solvent may be stirred using a rod, or a magnetic stirrer may be used, and the propeller-like stirrer may be rotated in one direction at a constant speed in the container. Usually the mixer is dissolved. Further, it may be dissolved by applying a shear force using a mixer, a dissolver or the like. It can also be heated and dissolved as needed.

In addition, it is also possible to use a two-roller, a three-roller, a ball mill, a drum sieve mill, a disperser, a kneader, a two-way kneader, a homogenizer, a blender, a single shaft or before using the beads for microdispersion. A biaxial extruder or the like performs kneading treatment while imparting a strong shearing force.

Further, details of the kneading and dispersion are described in "Attuit Flow and Pigment Dispersion" by TCPatton (John Wiley and Sons, 1964), and the like. The methods described therein can also be applied.

Further, in the dispersion, the following method is also a preferred embodiment in which the solid content in the dispersion composition is set to be higher than the solid content of the final dispersion composition at the initial stage of dispersion, and at a final timing close to the dispersion, The mixture is diluted with a component other than the coloring component such as an organic solvent or another polymer compound.

The method for preparing the dispersion composition is generally a preferred embodiment in which the dispersion is divided into two stages of coarse dispersion and precise dispersion, or further divided into a plurality of stages to carry out dispersion.

In other words, when the concentration of the specific dye in the dispersion composition at the initial stage of dispersion is Ci, and the concentration of the specific dye in the dispersion composition after the dispersion is completed (when the concentration is adjusted after the dispersion is completed, When the concentration of the specific dye after the concentration adjustment is Cf, the method of two-stage or more is dispersed so as to satisfy the relationship of Ci>Cf.

In the case of performing premixing, Ci is the concentration of the specific dye in the premixing; in the case where the premixing is not performed, Ci is the dispersion of the first stage in the two-stage dispersion or the multi-stage dispersion (the coarse in the two-stage dispersion) The concentration of the specific dye in the dispersion); in the case where the pre-mixing is not performed but the dispersion is performed in one stage, Ci is the concentration of the specific dye at the start of dispersion. Further, Cf is the concentration of the specific dye in the final stage of dispersion (precise dispersion in the two-stage dispersion), and when the concentration is adjusted after dispersion, the concentration of the specific dye after the concentration adjustment corresponds to the above Cf.

According to the above manner, at a high concentration, not only the dye is more easily adsorbed on the surface of the pigment, but also the pigment is slowly adsorbed on the surface of the pigment while the pigment is dispersed, and the adsorption equilibrium is achieved, and the dispersion is carried out, so that the adsorption rate can be improved. If Ci=Cf, even if the concentration adjustment is finally carried out, since the dye concentration is already low since the input, it takes time to reach the adsorption equilibrium, and depending on the case, the adsorption is inhibited by the dispersant or the additive, and there is a final The possibility of a decrease in the adsorption rate is therefore poor.

Further, according to this method, since the solid content is large at the initial stage of dispersion, a high shear force is applied to the dispersion liquid, and the pigment is easily dispersed by the shearing to obtain high dispersibility, which is a preferred embodiment.

Further, Ci is preferably set to 1.1 times to 10 times Cf, and particularly preferably 1.1 times to 5 times. By setting it as this range, the dispersion composition with high dispersibility can be acquired easily.

(other components contained in the dispersed composition)

Hereinafter, a dispersant and a pigment derivative which are preferably contained in the dispersion composition of the present invention will be described.

(Dispersant)

Specific examples of the dispersing agent include a plurality of compounds, and examples thereof include an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), a (meth)acrylic (co) polymer Polyflow No. 75, and Polyflow. No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusei Co., Ltd.) and other cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Non-ionics such as polyoxyethylene ether ether, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitol fatty acid ester Interface activator; anionic surfactant such as W004, W005, W017 (manufactured by Yushang Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (both manufactured by Ciba Specialty Chemical), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco) Molecular dispersant; Solsperse 3000, Solsperse 5000, Solsperse 9000, Solsperse 120 00, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 24000, Solsperse 26000, Solsperse 28000 and other Solsperse dispersants (made by Lubrizol Co., Ltd.); Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68, Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic F87, Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic L121, Adeka Pluronic P-123 (made by Asahi Kasei Co., Ltd.) and Eonet S-20 (made by Sanyo Chemical Co., Ltd.), Disperbyk 101, Disperbyk 103, Disperbyk 106, Disperbyk 108, Disperbyk 109, Disperbyk 111, Disperbyk 112, Disperbyk 116, Disperbyk 130, Disperbyk 140, Disperbyk 142, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 167, Disperbyk 170, Disperbyk 171, Disperbyk 174, Disperbyk 176, Disperbyk 180, Disperbyk 182, Disperbyk 2000, Disperbyk 2001, Disperbyk 2050, Disperbyk 2150 ( G Chemical (BYK-CHEMIE) Co., Ltd.).

- Polymer Dispersant -

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

The dispersion composition of the present invention is preferably a polymer compound containing at least one structural unit having at least one structural unit represented by the following formula (II) or the following formula (III) and having an acid group; (The following is sometimes referred to as "specific polymer").

In the above formula (II) and formula (III), 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 phenyl group, and L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and A ¹ and A ² each independently represent a monovalent organic group. 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 the general formula (II) or the general formula (III))

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

In the above formula (II) and formula (III), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably a substituted or unsubstituted alkyl group. 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, particularly preferably an alkyl group having 1 to 4 carbon atoms.

In the case where the alkyl group has a substituent, the substituent may, for example, be a hydroxyl group or an alkoxy group (preferably having a carbon number of 1 to 5, more preferably a carbon number of 1 to 3), a methoxy group, an ethoxy group or a ring. Hexyloxy and the like.

Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxyl groups. Propyl, 2-hydroxypropyl, 2-methoxyethyl.

R ¹ , R ² , R ⁴ and R ^{5 are} preferably a hydrogen atom, and R ³ and R ^{6 are} preferably a hydrogen atom or a methyl group in terms of the adsorption efficiency on the surface of the pigment.

X ¹ and X ² each independently represent -CO-, -C(=O)O-, -CONH-, -OC(=O)-, or a phenyl group. Among them, from the viewpoint of the adsorptivity of the pigment, -C(=O)O-, -CONH-, and a phenyl group are preferable, and -C(=O)O- is preferable.

L ¹ and L ² each independently represent a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group, or a divalent organic linking group formed by the alkylene group and a hetero atom or a partial structure containing a hetero atom. Here, the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, particularly preferably an alkylene group having 1 to 8 carbon atoms, particularly preferably an alkylene group having 1 to 4 carbon atoms. Further, examples of the hetero atom in the partial structure containing a hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. Among them, an oxygen atom and a nitrogen atom are preferable.

Specific examples of preferred alkylene groups include methylene, ethyl, propyl, trimethylene, and tetramethylene.

In the case where the alkylene group has a substituent, the substituent may, for example, be a hydroxyl group or the like.

In terms of the adsorption property to the pigment, the divalent organic linking group preferably has a terminal group selected from -C(=O)-, -OC(=O)-, -NHC(=O) at the terminal of the above alkylene group. a hetero atom or a partial structure containing a hetero atom, and via or A moiety in which a hetero atom is partially bonded to an adjacent oxygen atom.

A ¹ and A ² each independently represent a monovalent organic group. The monovalent organic group is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

Examples of preferred alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl Base, second butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2 - Lowering the base.

The substituent of the substituted alkyl group is a group using a monovalent non-metal atomic group from which hydrogen is removed, and preferred examples thereof include a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, Aryloxy, fluorenyl, alkylthio, arylthio, alkyldithio, aryldithio, amine, N-alkylamino, N,N-dialkylamino, N-aryl Amino, N,N-diarylamine, N-alkyl-N-arylamine, decyloxy, aminemethyloxy, N-alkylamine, methoxy, N-arylamine Methoxy, N,N-dialkylamine, methoxy, N,N-diarylamine, methoxy, N-alkyl-N-arylamine, methoxy, alkyl , aryl sulfhydryl, decyloxy, decylthio, decylamino, N-alkyldecylamino, N-aryldecylamino, ureido, N'-alkylureido, N',N'-dialkylureido, N'-arylureido, N',N'-diarylureido, N'-alkyl-N'-arylureido, N-alkyl Urea, N-arylureido, N'-alkyl-N-alkylureido, N'-alkyl-N-arylureido, N',N'-dialkyl-N-alkyl Urea, N', N'-dialkyl-N-arylureido, N'-aryl-N-alkylureido, N'-aryl-N-arylureido, N', N '-two Aryl-N-alkylureido, N',N'-diaryl-N-arylureido, N'-alkyl-N'-aryl-N-alkylureido, N'-alkane -N'-aryl-N-arylureido, alkoxycarbonylamino, aryloxycarbonylamino, N-alkyl-N-alkoxycarbonylamino, N-alkyl-N- Aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-aryl-N-aryloxycarbonylamino, decyl, decyl, carboxy, alkoxycarbonyl, aryl Oxycarbonyl, amine, mercapto, N-alkylamine, mercapto, N,N-dialkylamine, mercapto, N-arylamine, mercapto, N,N-diarylamine , N-alkyl-N-arylaminecarbamyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfo (-SO ₃ H) and Its conjugated base (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylamine sulfinyl group, N, N -dialkylamine sulfinyl, N-arylamine sulfinyl, N,N-diarylamine sulfinyl, N-alkyl-N-arylamine sulfinyl, amine sulfonate Sulfhydryl, N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-arylamine sulfonyl, N,N-diarylamine Acyl, N- alkyl -N- sulfo acyl aryl amines, phosphorus-acyl _{(phosphono) (- PO 3 H} 2) and its conjugate base (hereinafter referred to as phosphoric acid group), acyl dialkylphosphoryl (-PO ₃ (alkyl) ₂ ), diarylphosphonium (-PO ₃ (aryl) ₂ ), alkyl aryl phosphonyl (-PO ₃ (alkyl) (aryl), monoalkyl phosphonium (PO ₃ H(alkyl)) and its conjugated base (hereinafter referred to as alkyl phosphate group), monoarylphosphonium group (-PO ₃ H (aryl)) and its conjugated base (hereinafter referred to as An aryl phosphate group, a phosphonyloxy group (-OPO ₃ H ₂ ) and a conjugated base thereof (hereinafter referred to as a phosphoryloxy group), a dialkylphosphonium oxy group (-OPO ₃ (alkyl) ₂ ), diarylphosphonyloxy (-OPO ₃ (aryl) ₂ ), alkyl aryl phosphonyloxy (-OPO ₃ (alkyl) (aryl), monoalkylphosphoniumoxy (-OPO ₃ H(alkyl)) and its conjugated base (hereinafter referred to as alkylphosphooxy), monoarylphosphoniumoxy (-OPO ₃ H(aryl)) and its conjugated base (hereinafter referred to as arylphosphooxy), cyano, nitro, aryl, heteroaryl, alkenyl, alkynyl, decylalkyl.

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

In terms of dispersion stability, the substituent is preferably an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N,N-dialkylamino group, an N,N-diarylamino group, N-alkyl-N-arylamino, decyloxy, aryl, heteroaryl, alkenyl, alkynyl, decylalkyl.

Specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, and a chlorine group. Methylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxylated phenyl, benzhydryloxyphenyl, methylthiophenyl, phenyl Thiophenyl, methylaminophenyl, dimethylaminophenyl, ethenylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, ethoxyphenylcarbonyl, phenoxycarbonylbenzene A group, N-phenylamine, mercaptophenyl, phenyl, cyanophenyl, sulfophenyl, sulfophenyl, phosphonylphenyl, phenylphenyl, and the like.

In terms of dispersion stability and developability, A ¹ and A ^{2 are} preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and 5 carbon atoms. The cyclic alkyl group to 20 is more preferably a linear alkyl group having 4 to 15 carbon atoms, a branched alkyl group having 4 to 15 carbon atoms, and a cyclic alkyl group having 6 to 10 carbon atoms. It is preferably a linear alkyl group having 6 to 10 carbon atoms or a branched alkyl group having 6 to 12 carbon atoms.

m and n each independently represent an integer of 2-8. Dispersion stability and In terms of developability, m and n are preferably 4 to 6, and most preferably 5.

p and q each independently represent an integer from 1 to 100. Two or more types may be mixed with different p and different q. In terms of dispersion stability and developability, p and q are preferably from 5 to 60, more preferably from 5 to 40, and still more preferably from 5 to 20.

The specific polymer in the present invention contains at least one of the structural units represented by the above formula (II) or at least one of the structural units represented by the above formula (III), or contains the above formula (II). At least one of the structural units and at least one of the structural units represented by the above formula (III). Here, in the above formula (II) and formula (III), the following combinations are particularly preferred embodiments. That is, R ¹ , R ² , R ⁴ and R ^{5 are} preferably a hydrogen atom, and R ³ and R ^{6 are} preferably a hydrogen atom or a methyl group. X ¹ and X ^{2 are} preferably -C(=O)O-. L ¹ and L ² preferably have a hetero atom selected from -C(=O)-, -OC(=O)-, -NHC(=O)- at the terminal of the alkylene group having 1 to 4 carbon atoms. Or a partial structure containing a hetero atom and a divalent organic linking group bonded to an adjacent oxygen atom via the hetero atom or a partial structure containing a hetero atom. m and n are preferably 5, and p and q are preferably 5-20.

The specific polymer of the present invention is preferably a polymer containing at least one structural unit of the structural unit represented by the above formula (II) in terms of dispersion stability.

Further, the structural unit represented by the above formula (II) is more preferably a structural unit represented by the following formula (II)-2.

In the above formula (II)-2, R ¹ to R ³ each independently represent a hydrogen atom or a monovalent organic group, La represents an alkylene group having 2 to 10 carbon atoms, and Lb represents -C(=O)- or - NHC(=O)-, A ¹ represents a monovalent organic group, m represents an integer of 2-8, and p represents an integer of 1 to 100.

The details and preferred embodiments of the monovalent organic group represented by R ¹ to R ³ and A ¹ and m and p are the same as those in the above formula (II).

La is more preferably an alkylene group having 2 to 8 carbon atoms, and particularly preferably an alkylene group having 2 to 4 carbon atoms. Specific examples thereof include an ethyl group, a propyl group, a trimethylene group, and a tetramethylene group. In the case where the alkylene group has a substituent, the substituent may, for example, be a hydroxyl group or the like.

The structural unit represented by the above formula (II), formula (III) or formula (II)-2 is represented by the following formula (i), formula (ii) or formula (i)-2, respectively. The monomer shown is subjected to polymerization or copolymerization and introduced as a repeating unit of the polymer compound.

In the above formula (i), formula (ii) and formula (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 phenyl group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and La represents a carbon number of 2 ~10 alkylene, Lb represents -C(=O)- or -NHC(=O)-, A ¹ and A ² each independently represent a monovalent organic group, and m and n each independently represent 2-8 The integers, p and q, respectively, represent integers from 1 to 100, respectively.

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 and the above formula (II), formula (III) and formula (II) -2 has the same meaning.

Hereinafter, preferred examples of the monomer represented by the general formula (i), the general formula (ii) or the general formula (i)-2 [monomer (A-1) to monomer (A-24)], However, the present invention is not limited to these specific examples.

The specific polymer of the present invention contains at least one of the structural units represented by the above formula (II) or (III), and may be contained alone or in combination of two or more.

In addition, the content of the structural unit represented by the above formula (II) or formula (III) is not particularly limited, and in the case where the total structural unit contained in the polymer is 100% by mass, In view of the dispersibility and developability of the pigment, the above-mentioned structural unit is preferably contained in an amount of 5% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass to 60% by mass.

(structural unit having an acid group)

The specific polymer of the present invention comprises a structural unit having an acid group (acid group-containing) Structural unit). The acid group of the acid group-containing structural unit functions as an adsorption group for the pigment or the pigment derivative.

In the acid group-containing structural unit of the present invention, the acid group is preferably an acid group having a pKa of 10 or less. Specific examples of the acid group having a pKa of 10 or less include a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and a phenol group. Among them, a carboxylic acid group is most preferably used from the viewpoint of having both pigment dispersibility and developability.

In the acid group-containing structural unit of the present invention, the acid group 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 linked chain linking the main chain of the specific polymer to the acid group is preferably a linker containing a functional group selected from the group consisting of an aromatic ring, an ether group, an ester group, a decylamino group, a urea group, and/or a urethane group. base. Since the functional group exhibits adsorptivity to the pigment by itself, it is considered that in the structural unit containing an acid group, when the functional group is located close to the acid group, the effect of increasing the adsorption property to the pigment or the pigment derivative is obtained.

Here, the main chain of a specific polymer means a site which is bonded by polymerization when a polymer is synthesized. For example, a polymer obtained by polymerizing a methacrylate means a methyl methacrylate moiety. An alkyl group attached by polymerization.

Further, the above-mentioned linking group can be used in combination of a plurality of linking groups. For example, an aromatic ring and an ether group, an aromatic ring and an ester group, an aromatic ring and a urea group, an ether group and a urea group, an aromatic ring and an ether group, and a urea group can be used in combination.

In the case where the dispersion composition of the present invention contains titanium black as a pigment, since titanium black has a nitrogen atom, it is preferred to use a hydrogen-bonding functional group as a linking group of a specific polymer. Specifically, hydrazine is preferably used. Amino, ureido, urethane Ester group.

Further, it is preferred that the linking group used in the acid group-containing structural unit of the present invention is introduced into an aromatic ring. By having an aromatic ring in the linking chain, the entanglement of the polymer can be reduced by steric hindrance as compared with a usual alkyl chain or the like, and the aromatic ring is easily directed from the main chain portion toward the polymer, thereby improving the dispersibility of the pigment. .

Here, the aromatic ring means a structure in which atoms having π electrons are arranged in a ring shape, and a ring containing no hetero atom such as a benzene ring, a naphthalene ring or an anthracene ring, or a pyridine ring, a pyrrole ring, a furan ring or a carbazole can be used. Various rings such as a ring containing a hetero atom such as a ring or a thiophene ring. Among them, a benzene ring, a naphthalene ring, and a pyridine ring having high versatility can be suitably used, and a benzene ring can be more preferably used, and a structure represented by the following formula (2) is more preferable.

In the above formula (2), Y represents a linking group to a main chain of a specific polymer, and S represents an acidic functional group. R represents 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, An alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, a alkylguanamine group which may have a substituent, may have A substituted arylamine group, a halogen group, a nitro group. Further, n represents an integer of 0 to 4, and m represents an integer of 1 to 5.

In the above formula (2), Y represents a linking group to a main chain of a specific polymer. The structure of the linking group is not particularly limited. From the viewpoint of lowering the pKa of the acid group, it is preferred to bond the benzene ring and the main chain with an electron-withdrawing group, and more preferably an ester group, a guanamine group or a sulfonamide group. It is more preferable to link by an ester group.

Preferred specific examples of Y are shown below, but Y is not limited to these structures. X represents a site to which a main polymer is bonded, and Z represents a site to which a benzene ring is bonded.

In the above formula (2), R represents 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, may have a substitution. a heteroaryloxy group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, a alkylguanamine group which may have a substituent, An arylguanamine group, a halogen group, or a nitro group which may have a substituent. From the viewpoint of lowering the pKa of the acid group, it is preferably a hydrogen atom or an electron withdrawing group, and is preferably a hydrogen atom, an alkoxycarbonyl group which may have a substituent, and an aryloxycarbonyl group which may have a substituent. An alkylguanamine group which may have a substituent, an arylguanamine group which may have a substituent, a halogen group, a nitro group, a carboxyl group, and more preferably a hydrogen atom, an alkoxycarbonyl group which may have a substituent, may have A substituted aryloxycarbonyl group.

The acid group-containing structural unit of the present invention is preferably a structural unit having a carboxylic acid group as an acid group (hereinafter sometimes referred to as "a structural unit containing a carboxylic acid group"). More preferably, it is a structural unit having a carboxylic acid group bonded to a main chain of a specific polymer via a linking chain containing an atomic group having four or more atoms other than a hydrogen atom.

In the structural unit containing a carboxylic acid group, a carboxylic acid group is bonded to the main chain via a linking chain, whereby the flexibility of the carboxylic acid group portion is improved, and the pigment or the pigment derivative can be more efficiently interacted. Further, since the carboxylic acid group also functions as a developable group, the flexibility is improved, and the developability is also improved. In this respect, the longer the link chain, the better.

On the other hand, when the linking chain is too long, the number of structural units containing a carboxylic acid group which can be introduced into the polymer is small, and therefore, the amount of the carboxylic acid group which can be introduced into the polymer is small.

According to the above, in the structural unit containing a carboxylic acid group, it is preferred that the linking chain linking the main chain and the carboxylic acid group contains an atomic group having 4 to 100 atoms other than the hydrogen atom, and more preferably contains hydrogen. The number of atoms other than an atom is 6 to 60, and particularly preferably an atom having 8 to 20 atoms other than a hydrogen atom. group.

In the structural unit containing a carboxylic acid group, a preferred embodiment of the linking chain in which the main chain of the specific polymer and the carboxylic acid group are bonded is the same as the linking chain in the acid group-containing structural unit, and the same applies to A plurality of linking groups can be used in combination as a linking chain.

The linking group used in the structural unit containing a carboxylic acid group is the same as the structural unit containing the acid group, and it is preferred to introduce an aromatic ring. The preferred embodiment of the aromatic ring is also the same.

The partial structure of the above structural unit containing a carboxylic acid group is more preferably a structure represented by the following formula (1).

In the above formula (1), Y, R, and n have the same meanings as in the above formula (2). The carboxylic acid group can be introduced from the benzene ring via a linking group.

Specific examples of the partial structure represented by the above formula (1) are shown below, but the partial structure is not limited to these specific examples. X represents a binding site to the main chain.

In the structural unit containing a carboxylic acid group, it is preferred that the linking chain includes an atomic group having an aromatic ring and having 6 or more and 60 or less atoms other than a hydrogen atom. More preferably, the aromatic ring is a benzene ring, and is bonded to the main chain via the benzene ring or an ester bond.

In the specific polymer of the present invention, the content of the carboxylic acid group-containing structural unit is preferably 50 mgKOH/g or more in terms of acid value in terms of suppressing the formation of precipitates in the developer in the formation of the colored region. In order to effectively suppress aggregates of primary particles that form pigments (ie, secondary aggregates), or to effectively weaken the condensation of secondary aggregates The content of the carboxylic acid group-containing structural unit is preferably from 50 mgKOH/g to 200 mgKOH/g in terms of acid value.

(other structural units)

The specific polymer of the present invention is preferably a polymer compound obtained by further copolymerizing a monomer having a functional group adsorbable on the pigment for the purpose of improving the adsorption property to the pigment.

In addition to the acid group, the monomer having a functional group which can be adsorbed on the pigment may specifically be a monomer having an organic dye structure or a heterocyclic structure, a monomer having a basic nitrogen atom, and a single having an ionic group. Body and so on. Among them, in terms of the adsorption force to the pigment, a monomer having an organic dye structure or a heterocyclic structure is preferred.

The monomer having a functional group that can be adsorbed on the pigment can be appropriately selected depending on the type of the pigment to be dispersed, and these monomers may be used singly or in combination of two or more kinds.

The specific polymer of the present invention may further contain a structural unit derived from a copolymerizable vinyl monomer, within a range not impairing the effect thereof.

The vinyl monomer which can be used herein is not particularly limited, and for example, preferred are (meth)acrylates, butenoates, vinyl esters, maleic acid diesters, and antibutene. Acid diesters, methylene succinic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile, and the like. Specific examples of such a vinyl monomer include the following compounds. In addition, in the case of either or both of "acryloyl methacrylic acid and methacryl fluorenyl group", it may be described as "(meth)acryl fluorenyl group".

Examples of the (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (methyl). N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butyl (meth)acrylate Cyclohexyl ester, 2-ethylhexyl (meth)acrylate, third octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, (A) Ethyl ethoxide ethyl acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethyl (meth) acrylate Oxyethyl ester, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, Diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl (meth)acrylate, (meth)acrylic acid polyethylene glycol monomethyl ether, (meth)acrylic acid poly Glycol monoethyl ether, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, (methyl) Dicyclopentenyloxyethyl acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctyl (meth)acrylate, (meth)acrylic acid Cyclopentyl ester, tribromophenyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, and the like.

Examples of the crotonates include butyl butenoate and hexyl butenoate.

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

Examples of the maleic acid diesters include dimethyl maleate, Diethyl maleate, dibutyl maleate, and the like.

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

Examples of the methylene succinic acid diesters include dimethyl methylene succinate, diethyl methylene succinate, and dibutyl methylene succinate.

Examples of the (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl (methyl). Acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl ( Methyl) acrylamide, N-(2-methoxyethyl)(methyl) acrylamide, N,N-dimethyl(meth) decylamine, N,N-diethyl (A Base) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) propylene hydrazino, diacetone acrylamide, and the like.

Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, and methoxy. Styrene, butoxy styrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, a group deprotected with an acidic substance (e.g., t-butoxycarbonyl (t-Boc), etc.) protected by hydroxystyrene, methyl benzoate, and α-methylstyrene.

Specific examples of the specific polymer of the present invention include the following exemplified combinations Compound 1 - exemplified compound 35.

The preferred molecular weight of the specific polymer of the present invention is in the range of 5,000 to 100,000 in terms of weight average molecular weight (Mw) and in the range of 2,500 to 50,000 in terms of number average molecular weight (Mn). More preferably in terms of weight average molecular weight (Mw) The range of 10,000 to 50,000 is in the range of 5,000 to 30,000 in terms of the number average molecular weight (Mn). In particular, it is preferably in the range of 20,000 to 40,000 in terms of weight average molecular weight (Mw) and in the range of 5,000 to 20,000 in terms of number average molecular weight (Mn).

That is, the weight average molecular weight (Mw) of the specific polymer is preferably 1,000 or more from the viewpoint of effectively dissolving the aggregate of the primary particles of the pigment (that is, the secondary aggregate) or effectively weakening the re-agglomeration. In addition, the weight average molecular weight (Mw) of the specific polymer is preferably 50,000 or less from the viewpoint of developability when producing a color filter using a colored photosensitive composition containing a dispersion composition.

The specific polymer of the present invention can be produced by a usual radical polymerization method.

A suspension polymerization method or a solution polymerization method or the like is usually used. Examples of the solvent used in the synthesis of the above specific polymer include dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, and ethylene. Alcohol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N - dimethyl acetamide, dimethyl hydrazine, toluene, ethyl acetate, methyl lactate, ethyl lactate, and the like. These solvents may be used singly or in combination of two or more. Further, a radical polymerization initiator may be used in the radical polymerization, and a chain transfer agent (for example, 2-mercaptoethanol and dodecylmercaptan) may be further used.

The content of the dispersant in the dispersion composition is preferably a pigment: a specific polymer (mass ratio) = 1:0.1 to 1:2, more preferably 1:0.2 to 1:1, and particularly preferably 1: Range of 0.4~1:0.7.

Further, the dispersion composition may contain a pigment derivative.

The term "pigment derivative" refers to a compound in which an acidic group, a basic group, or an aromatic group is introduced as a substituent in a side chain of an organic pigment, and is different from a specific dye.

In the present invention, the blue pigment adsorbs a specific dye on the surface thereof, and the pigment derivative having a moiety having affinity with the specific polymer (polymer dispersant) can be adsorbed to a specific dye which is not adsorbed. The surface of the pigment is used as a point of adsorption of a specific polymer, so that the pigment is further dispersed as fine particles in the coloring composition. In addition, it can also prevent re-agglomeration. That is, the pigment derivative has an effect of promoting adsorption of a polymer dispersant such as a specific polymer of the present invention by modifying the surface of the pigment to which the specific dye is not adsorbed.

Since the specific polymer of the present invention has an acid group, by using a basic pigment derivative having a basic group as a pigment derivative, the dispersibility of the pigment is further improved, and the fine pigment can be efficiently dispersed. Further, by using the colored photosensitive composition containing a basic pigment derivative, a color filter having small color density unevenness and excellent color characteristics can be further formed.

The pigment derivative is a compound in which an organic pigment is used as a matrix and an acidic group or a basic group or an aromatic group is introduced as a substituent in a side chain. Specifically, examples of the organic pigment to be the matrix of the parent include quinacridone pigment, phthalocyanine pigment, azo pigment, quinophthalone pigment, and isoindoline. Pigment, isoindolinone pigment, quinoline pigment, diketopyrrolopyrrole pigment, benzimidazolone Materials and so on. Further, the parent skeleton also contains a pale yellow aromatic polycyclic compound such as a naphthalene, an anthracene, a triazine or a quinoline which is not normally referred to as a dye.

For the pigment derivative, the pigment derivative described in the following patent documents can be used: Japanese Patent Laid-Open No. Hei 11-49974, Japanese Patent Laid-Open No. Hei 11-189732, Japanese Patent Laid-Open No. Hei 10-245501, and Japanese Patent Laid-Open Publication No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. -356210, etc.

When a pigment derivative is used in the dispersion composition of the present invention, the amount of the pigment derivative used is preferably in the range of 1% by mass to 80% by mass, more preferably 3% by mass based on the pigment. In the range of 65 mass%, it is particularly preferably in the range of 5 mass% to 50 mass%. When the content is within this range, the dispersion of the pigment can be favorably performed while suppressing the viscosity to a low value, and the dispersion stability after dispersion can be improved. Further, by applying the colored photosensitive composition to the production of a color filter, a color filter having high transmittance, excellent color characteristics, and high contrast can be obtained.

Further, other polymer compounds may be used in addition to the specific polymer of the present invention, as long as the effects of the present invention are not impaired. Other polymer compounds are natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like.

The natural resin is representatively rosin, and the modified natural resin can be exemplified by: pine Fragrance derivatives, cellulose 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. The synthetic resin modified by the natural resin may, for example, be a rosin-modified maleic acid resin or a rosin-modified phenol resin.

The synthetic resin may, for example, be a polyamine amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a polyurethane, a polyester, a poly(meth)acrylate, or a (meth)acrylic acid. A copolymer, a formalin condensate of naphthalenesulfonate.

The content of the blue pigment in the dispersion composition is preferably 20% by mass to 70% by mass, and more preferably 30% by mass to 60% by mass based on the total solid content (mass) of the dispersed composition. When the content of the blue pigment is within the above range, it is effective for ensuring color characteristics that are sufficiently excellent in color density.

Further, the content of the specific dye in the dispersion composition is preferably from 5% by mass to 40% by mass, and more preferably from 10% by mass to 30% by mass based on the total solid content (mass) of the dispersed composition. When the content of the specific dye is within the above range, the dispersion stability of the dispersion composition is good, and it is effective for ensuring color characteristics which are sufficiently excellent in color density.

In addition, the content of the blue pigment in the coloring photosensitive composition of the present invention is preferably from 1% by mass to 50% by mass, and more preferably from 1% by mass to 30% by mass, based on the total solid content of the composition.

Further, the content of the specific dye in the colored photosensitive composition of the present invention is preferably from 0.1% by mass to 25% by mass based on the total solid content of the composition. Preferably, it is 0.1% by mass to 15% by mass. When the content of the pigment and the specific dye is within the above range, the coloring layer obtained by using the coloring photosensitive composition has high luminance and high contrast, and it is easy to satisfy various characteristics required for coloring photosensitive composition such as developability.

[(C) Polymerizable Compound]

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

The polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected from known components constituting the composition, and the paragraph number [0010] of JP-A-2006-23696 is exemplified. The components described in [0020] or the components described in paragraphs [0027] to [0053] of JP-A-2006-64921.

In addition, a urethane-added polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also preferred, as disclosed in Japanese Laid-Open Patent Publication No. SHO-51-37193, and Japanese Patent Publication No. 2-32293. The urethane acrylates described in Japanese Patent Publication No. 2-16765, or Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, and Japanese Patent Publication No. SHO 62-39417 A urethane compound having an oxirane skeleton described in Japanese Patent Publication No. Sho 62-39418 is also preferred.

Other examples include polyester acrylates described in each of the publications of JP-A-48-64183, JP-A-49-43191, and Japanese Patent Publication No. Sho 52-30490. Oxygen resin and (meth)acrylic acid A polyfunctional acrylate or methacrylate such as an epoxy acrylate obtained by the reaction. Further, it can be used as an example of photocurable monomers and oligomers in Japanese Journal of Adhesives, Vol. 20, No. 7, pp. 300-308 (1984).

Specific examples thereof include the following compounds: pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and three ((meth)acrylomethoxyethyl)isocyanurate, ethylene oxide (EO) modified by pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate EO modified body, etc.; and commercially available products, namely NK Ester A-TMMT, NK Ester A-TMM-3, NK Oligo UA-32P, NK Oligo UA-7200 (above manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix M-402, Aronix TO-1382, Aronix TO-2349 (above manufactured by East Asia Synthetic Co., Ltd.), V#802 (Osaka Organic Chemical Industry (stock) manufacturing).

Further, the compound described in Paragraph Nos. [0031] to [0061] of JP-A-2009-265630 is also preferable, and among them, the following compounds described in [0055] to [0059] are preferable.

These polymerizable compounds may be used singly or in combination of two or more.

The content of the polymerizable compound in the total solid content in the coloring photosensitive composition (the total content in the case of two or more kinds) is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 75% by mass. , particularly preferably from 20% by mass to 60% by mass.

[(D) Photopolymerization initiator]

The colored photosensitive composition of the present invention preferably contains at least one photopolymer Starter.

The photopolymerization initiator is not particularly limited as long as it is an initiator capable of polymerizing the above polymerizable compound, and is preferably selected from the viewpoints of characteristics, initial efficiency, absorption wavelength, availability, cost, and the like.

The photopolymerization initiator is a compound which initiates and accelerates polymerization of a polymerizable compound by being exposed to light by exposure light. It is preferably a compound which initiates and accelerates polymerization of a polymerizable compound by inducing active light having a wavelength of 300 nm or more. Further, a photopolymerization initiator which does not directly induce active light having a wavelength of 300 nm or more may be preferably used in combination with a sensitizer.

Specific examples thereof include an oxime ester compound, an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, and an acridine compound. , organic peroxide, azo compound, coumarin compound, azide compound, metallocene compound, hexaaryl biimidazole compound, organoboric acid compound, disulfonate An acid compound, an onium salt compound, an acyl phosphine (oxide), a benzophenone compound, an acetophenone compound, and a derivative thereof.

Among these compounds, an oxime ester compound or a hexaarylbiimidazole compound is preferred in terms of sensitivity.

As the oxime ester compound, a compound described in the following patent documents can be used: Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2001-233842, Japanese Patent Publication No. 2004-534797, International Publication No. 2005/080337, International Publication No. 2006/018973, Japanese Patent Laid-Open No. 2007-210991, Japanese Patent Laid-Open No. 2007-231000, Japanese Patent Japanese Patent Publication No. 2007-269779, Japanese Patent Laid-Open No. 2009-191061, and International Publication No. 2009/131189.

Specific examples include 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)肟)-1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)benzene 1,1,2-hexanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(O -benzylidene hydrazide)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-benzylidene fluorenyl)-1-[4-(A Phenylthio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(ethylphenylthio)phenyl]-1,2 -butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(butylphenylthio)phenyl]-1,2-butanedione, 1-(O-ethenyl)肟)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[ 9-Methyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-propyl-6 -(2-methylbenzimidyl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-ethyl Benzyl hydrazino)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-butylbenzylidene)- 9H-carbazol-3-yl]ethanone and the like. However, it is not limited to these examples.

In the present invention, the compound represented by the following formula (A) is also suitable as a photopolymerization initiator (i.e., a oxime ester compound) from the viewpoints of sensitivity, stability over time, and coloration in heat resistance. ).

In the 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. 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 arylalkyl group or a heterocyclic group, and these groups may be substituted by one or more selected from the group consisting of a halogen atom and a heterocyclic group. One or more carbon atoms of the alkyl chain in the alkyl group and the aralkyl group 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 the general formula (A), examples of the halogen atom in the case where X ¹ , X ² and X ³ represent a halogen atom include fluorine, chlorine, bromine and iodine, and in the case where X ¹ , X ² and X ³ represent an alkyl group, Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a third pentyl group, and a hexyl group. , heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, Propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, A Oxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazole-2'-yl)vinyl, and the like.

In particular, it is preferred that X ¹ , X ² and X ³ each represent a hydrogen atom, or X ¹ represents an alkyl group and both X ² and X ³ represent a hydrogen atom.

In the general formula (A), examples of the alkyl group represented by R and R' include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a t-butyl group. Pentyl, isopentyl, third amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, ethylene Base, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxy Ethyl, propoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazole -2'-yl) vinyl and the like.

Examples of the aryl group represented by R and R' include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group.

Examples of the aralkyl group represented by R and R' include a benzyl group, a chlorobenzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, and a phenylvinyl group.

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

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

In a particularly preferred embodiment, R ² and R ³ each comprising R and R′ are independently methyl, hexyl, cyclohexyl, —S—Ph, —S—Ph—Cl, and —S—Ph-Br. .

Among the photopolymerization initiators, those which are particularly suitable as photopolymerization initiators are those in which X ¹ , X ² and X ³ in the formula (A) are each a hydrogen atom; R ¹ is an alkyl group, particularly a methyl group; ² is an alkyl group, especially a methyl group; and R ³ is an alkyl group, especially an ethyl group.

Therefore, preferred examples of the photopolymerization initiator represented by the above 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 formula (A) can be synthesized, for example, by the method described in JP-A-2005-220097.

The compound represented by the formula (A) used in the present invention is a compound having an absorption wavelength in a wavelength region of from 250 nm to 500 nm. More preferably, it is a compound having an absorption wavelength in a wavelength range of 300 nm to 380 nm. Particularly preferred are compounds with high absorbance at 308 nm and 355 nm.

In the present invention, the oxime ester compound as a photopolymerization initiator is also preferably represented by the following formula (B) from the viewpoints of sensitivity, stability over time, and coloration upon post-heating. Compound.

In the 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 from 0 to 5. X ²² represents a monovalent substituent, and in the case where n is an integer of 2 to 4, a plurality of X ²² may be the same or different.

The monovalent substituent represented by the above R ²² is preferably a monovalent non-metal atom group shown below.

The monovalent non-metal atom group represented by R ²² may, for example, be 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 mercapto 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 hexylcyclopentyl 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, for example, Listed: phenyl, biphenyl, 1-naphthyl, 2-naphthyl and the like.

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.

The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 20 carbon atoms, and examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a trifluoromethylcarbonyl group, a amyl group, a benzamidine group, and a group. Naphthylmethyl, 2-naphthylmethyl, 4-methylsulfanylbenzylidene, 4-phenylsulfanylbenzylidene, 4-dimethylaminobenzimidyl, 4- Diethylaminobenzimidyl, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzylidene, 3-chloro Benzopyridyl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyanobenzylidene , 4-methoxybenzhydryl and the like.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. For example, a thienyl group, a furyl group, a piperidyl group, etc. are mentioned.

In terms of high sensitivity, the above R ^{22 is more} preferably an unsubstituted or substituted fluorenyl group, and particularly preferably an unsubstituted or substituted ethyl fluorenyl group, a propyl fluorenyl group, Benzopyridinyl, toluylcarbenyl.

The substituent represented by the following structural formula is, for example, any of (d-1), (d-4) and (d-5).

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

Examples of the substituent which can be introduced into the group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group, and a phenoxy group. An aryloxy group such as a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; and the like.

Wherein, in terms of improving the sensitivity and suppressing the coloring caused by the passage of the heating time, the above A ^{22 is} preferably an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a third butyl group). , dodecyl) substituted alkylene, alkylene substituted by alkenyl (eg vinyl, allyl), aryl (eg phenyl, p-tolyl, xylyl, isopropyl) Phenyl, naphthyl, anthracenyl, phenanthryl, styryl) substituted alkylene.

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

Specifically, Ar may be exemplified by phenyl, biphenyl, 1-naphthyl, 2-naphthyl, triphenyl, biphenyl, o-tolyl, m-tolyl, p-tolyl, xylene Base, o-isopropylphenyl, m-isopropylphenyl, and p-cumyl, mesityl and the like. Among them, a substituted or unsubstituted phenyl group is preferred in terms of improving the sensitivity and suppressing the coloration caused by the passage of the heating time.

When the phenyl group has a substituent, the substituent may, for example, be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, or an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group. An aryloxy group such as a phenoxy group or a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; an ethoxy group, a propenyloxy group, a benzamidine group or the like. An alkyl group such as an anthracene group, an ethyl fluorenyl group, a benzamidine group, an isobutyl group, an acryl fluorenyl group, a methacryl fluorenyl group, a methoxalyl group, a methyl group or a cyclohexylamino group. a dialkylamino group such as an amine group, a dimethylamino group, a diethylamino group, a morpholinyl group or a piperidinyl group, a phenylamino group, a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, etc. Alkyl group, hydroxyl group, carboxyl group, and the like.

In the general formula (B), when the structure of "SAr" formed of the above Ar and the adjacent S is as follows, it is preferable in terms of sensitivity.

The monovalent substituent represented by the above X ²² may, for example, be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent which may have a substituent An alkoxy group, 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 halogen atom, etc.

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, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group, and 2 -ethylhexyl, benzamidine methyl 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 tetraphenyl group, and an adjacent group. Tolyl, m-tolyl, p-tolyl, xylyl and the like.

The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

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, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a benzyloxy group, and the like. .

The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, and examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenoxy group, and a 2- Methylphenoxy, 2-methoxyphenoxy and the like.

The alkylthiooxy group which may have a substituent is preferably a thioalkyloxy group having 1 to 30 carbon atoms, and examples thereof include a methylthiooxy group, an ethylthiooxy group, and a propylthiooxy group. , isopropylthiooxy, butylthiooxy, isobutylthiooxy, second butylthiooxy, tert-butylthiooxy, pentylthiooxy, iso Pentylthiooxy, hexylthiooxy, heptylthiooxy, octylthiooxy, 2-ethylhexyl Alkylthiooxy, decylthiooxy, dodecylthiooxy, octadecylthiooxy, benzylthiooxy and the like.

The arylthiooxy group which may have a substituent is preferably an arylthiooxy group having 6 to 30 carbon atoms, and examples thereof include a phenylthiooxy group, a 1-naphthylthiooxy group, and a 2-naphthyl group. Thiooxy, 2-chlorophenylthiooxy, 2-methylphenylthiooxy, 2-methoxyphenylthiooxy, 2-butoxyphenylthiooxy, 3-chlorophenylthiooxy, 3-trifluoromethylphenylthiooxy, 3-cyanophenylthiooxy, 3-nitrophenylthiooxy, 4-fluorophenyl Thiooxy, 4-cyanophenylthiooxy, 4-methoxyphenylthiooxy, 4-dimethylaminophenylthiooxy, 4-methylsulfanylbenzene Alkylthiooxy, 4-phenylsulfanylphenylthiooxy, and the like.

The halogen atom has a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like.

The halogenated alkyl group which may have a substituent may, for example, be a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group or a tribromomethyl group. Wait.

Examples of the guanamine group which may have a substituent on N include an N,N-dimethylammonium group, an N,N-diethylguanamine group, and the like.

Among these groups, X ^{22 is} preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, may have a substituent, in terms of improvement in solvent solubility and absorption efficiency in a long wavelength region. Alkenyl group, alkynyl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylthiooxy group which may have a substituent, arylthio group which may have a substituent An oxy group, a halogenated alkyl group which may have a substituent, an amine group which may have a substituent, or a guanamine group which may have a substituent on N, and more preferably an alkyl group which may have a substituent.

Further, n in the general formula (B) represents an integer of 0 to 5, and is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2, from the viewpoint of easiness of synthesis.

In the general formula (B), when a plurality of X ²² are present, the plurality of X ²² may be the same or different.

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

The compound represented by the formula (B) used in the present invention is a compound having an absorption wavelength in a wavelength region of from 250 nm to 500 nm. More preferably, it is a compound having an absorption wavelength in a wavelength range of 300 nm to 380 nm. Particularly preferred are compounds with high absorbance at 308 nm and 355 nm.

Specific examples of the organic halogenated compound include: Bulling et al., Bulletin of the Chemical Society of Japan, Bull Chem. Soc. Japan, Vol. 42, pp. 2924 (1969), U.S. Patent Japanese Patent No. 3,905,815, Japanese Patent Publication No. Sho 46-4605, Japanese Patent Laid-Open No. SHO-48-36281, Japanese Patent Laid-Open No. Sho 55-32070, Japanese Patent Laid-Open Publication No. SHO-60-239736, Japanese Patent JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, and JP-A-63-70243 Japanese Laid-Open Patent Publication No. SHO63-298339, MP Hutt, "Journal of Heterocyclic Chemistry" 1 (No. 3) (1970), etc.; A substituted oxazole compound or a s-triazine compound.

Examples of the hexaarylbiimidazole compound include, for example, various compounds described in the respective specifications, such as Japanese Patent Publication No. Hei. 6-29285, U.S. Patent No. 3,479,185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286. Is: 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-chlorophenyl)-4,4',5,5'-tetrakis(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'-double (o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole and the like.

The photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds of photopolymerization initiators are used, a plurality of compounds represented by the formula (B) can be used, and a plurality of compounds represented by the formula (II) can also be used. Further, at least one of the compounds represented by the general formula (II) and the general formula (III) may be used. In addition, at least one of the compounds represented by the general formula (II) and the general formula (III), and other than the hydrazine compound or the hydrazine compound other than the compound represented by the general formula (II) and the general formula (III). Photopolymerization initiator. In addition, a sensitizer may also be used in combination.

The total content of the photopolymerization initiator is preferably from 0.1% by mass to 20% by mass, more preferably from 0.5% by mass to 20% by mass, most preferably from 1% by mass to the total solid content of the coloring photosensitive composition. 10% by mass. If it is in this range, the sensitivity at the time of exposure is high, and the color characteristics are also favorable.

<(E) Alkali Soluble Binder>

In the colored photosensitive composition of the present invention, in order to improve film formability, an alkali-soluble binder is preferably used from the viewpoint of pattern formability.

The alkali-soluble binder is not particularly limited as long as it has alkali solubility, and is preferably selected from the viewpoints of heat resistance, developability, and availability.

The alkali-soluble binder is preferably a linear organic high molecular polymer, and is a polymer which is soluble in an organic solvent and can be developed with a weak aqueous alkali solution. Such a line Examples of the organic polymer include a polymer having a carboxylic acid in a side chain, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, Japanese Patent Publication No. Sho 58-12577, Japan The methacrylic acid copolymer, the acrylic copolymer, and the methylene succinic acid copolymer described in each of the publications of Japanese Patent Laid-Open Publication No. Sho 59-53836, and Japanese Patent Laid-Open Publication No. 59-71048 As the acid, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer or the like, an acidic cellulose derivative having a carboxylic acid in a side chain can also be used.

In addition to the above polymers, an alkali-soluble binder may be used: a polymer having an acid anhydride added to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polyoxyalkylene resin, or a poly(methyl group). ) 2-hydroxyethyl acrylate), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol, and the like. Further, the linear organic high molecular polymer may be a polymer obtained by copolymerizing a monomer having hydrophilicity. Examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth) acrylate, (meth) acrylamide, and N-methylol propylene oxime. Amine, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinyl pyrrolidone, N-vinyl hexene Indoleamine, vinylimidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, branched or linear (methyl) Butyl acrylate or phenoxy hydroxypropyl (meth)acrylate. Further, the hydrophilic monomer may also contain a tetrahydroindenyl group, a phosphoric acid group, a phosphate group, a quaternary ammonium salt group, an extended ethyloxy chain, a propyloxy chain, a sulfonic acid group, and a source thereof. a monomer formed by a salt group, a morpholinylethyl group or the like.

Further, in order to improve the crosslinking efficiency, the alkali-soluble binder may have a polymerizable group in the side chain, and for example, an allyl group, a (meth)acryl fluorenyl group, an allyloxyalkyl group, or the like may be used in the side chain. Polymers, etc. Examples of the polymerizable group-containing polymer include a Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.) and Photomer 6173 (a COOH-containing polyurethane urethane oligomer). , Diamond Shamrock Co. Ltd., manufactured by Viscoat R-264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, and Placcel CF200 series (both by Ebecryl 3800 (manufactured by Daicel-UCB). Further, in order to increase the strength of the hardened film, an alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin may be used.

Among these various alkali-soluble binders, from the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, and an acrylonitrile/acrylonitrile are preferable. The amine copolymer resin is preferably an acrylic resin, an acrylamide resin, or an acrylonitrile/acrylamide copolymer resin from the viewpoint of developability control.

The acrylic resin is preferably a copolymer containing a monomer selected from the group consisting of benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, (meth)acrylamide, and the like, or The above Photomer 6173, KS Resist-106, Cyclomer P series, and the like.

The alkali-soluble binder preferably has a weight average molecular weight (polystyrene-converted value measured by a gel permeation chromatography (GPC) method) of 1000 to 2 × 10 in terms of developability, liquid viscosity, and the like. The polymer of ⁵ is more preferably a polymer of 2000 to 1 × 10 ⁵ , particularly preferably a polymer of 5000 to 5 × 10 ⁴ . They may be used alone or in combination of two or more.

<Other ingredients>

The colored photosensitive composition of the present invention may further contain a known additive as long as the effect of the present invention is not impaired, for example, a polyfunctional thiol compound, a chain transfer agent, a polymerization inhibitor, an organic solvent, or an interface. Active agent, adhesion improver, crosslinking agent, development accelerator, and other additives.

The components are described below.

(multifunctional thiol compound)

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

The colored photosensitive composition of the present invention contains a polyfunctional thiol compound to improve sensitivity, suppress ion elution by a colored material such as a dye, and the like, and uses the coloring of the present invention in color filter production of a liquid crystal display device. In the case of a photosensitive composition, deterioration in image quality such as crosstalk can be prevented, and a clear high-quality display can be performed.

The "polyfunctional thiol compound" in the present invention means a compound having two or more thiol groups in the molecule. The polyfunctional thiol compound is preferably a low molecular compound having a molecular weight of 100 or more. Specifically, the molecular weight is preferably from 100 to 1,500, particularly preferably from 150 to 1,000. The above polyfunctional thiol compound preferably has 2 in the molecule More than 10 thiol groups, particularly preferably having 2 to 6 thiol groups. Further, these compounds are preferably used as a system for assisting use in the polymerization of the above-mentioned radical polymerizable monomer. Specifically, the amount of the polyfunctional thiol compound to be added is preferably 1% by mass to 20% by mass based on the total solid content of the composition, or the addition of the above-mentioned radical polymerizable monomer is preferably contained. A small amount of addition.

Specific examples of the polyfunctional thiol compound which can be used in the present invention include, for example, the following compounds as preferred polyfunctional thiol compounds: trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercapto) Propionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetra(thioglycolate), pentaerythritol tetrakis(3-mercaptobutyrate) ), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1 , 3,5-triazine-2,4,6(1H,3H,5H)-trione and the like.

The content of the polyfunctional thiol compound is preferably from 0.01% by mass to 20% by mass, particularly preferably from 0.1% by mass to 10% by mass, based on the total solid content of the coloring photosensitive composition. When the content of the polyfunctional thiol compound is within this range, the sensitivity of the colored photosensitive composition is good, the storage stability is good, and the adhesion of the pixels in the obtained color filter is good and there is no pattern defect, and it can be provided for use. A colored photosensitive composition having excellent electrical characteristics in the case of a liquid crystal display device.

(sensitizer)

A sensitizer may be added to the colored photosensitive composition of the present invention. Typical sensitizers used in the present invention are Crivello [J.V. Crivello, Advances in Polymer Science, Adv. in Polymer Sci, Vol. 62 Specific examples of the sensitizer disclosed in the first issue (1984) include: pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone. ), benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene ), camphorquinone, phenothiazine derivatives, and the like. The sensitizer is preferably added in a proportion of 50% by mass to 200% by mass based on the photopolymerization initiator.

(chain transfer agent)

A chain transfer agent may also be added to the colored photosensitive composition of the present invention. The chain transfer agent used in the present invention may, for example, be an N,N-dialkylaminobenzoic acid alkyl ester such as N,N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, or 2- A mercapto compound having a heterocyclic ring such as mercaptobenzoxazole, 2-mercaptobenzimidazole or N-phenylmercaptobenzimidazole.

The chain transfer agent may be used singly or in combination of two or more.

The amount of the chain transfer agent added is preferably in the range of 0.01% by mass to 15% by mass, more preferably 0.1% by mass, based on the total solid content of the coloring photosensitive composition of the present invention, from the viewpoint of reducing the sensitivity unevenness. ~10% by mass, particularly preferably 0.5% by mass to 5% by mass.

(polymerization inhibitor)

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

The term "polymerization inhibitor" refers to a substance which exhibits an action of hydrogenating a polymerization starting species such as a radical generated in a coloring photosensitive composition by light or heat. Supply (or hydrogen donation), energy supply (or energy transfer), electron supply (or electron donation), etc., inactivate the polymerization starting species, and inhibit the polymerization that is initiated inadvertently. A polymerization inhibitor or the like described in paragraphs 0154 to 0173 of JP-A-2007-334322 can be used.

Among these, the polymerization inhibitor is preferably p-methoxyphenol.

The content of the polymerization inhibitor in the coloring photosensitive composition of the present invention is preferably 0.0001% by mass to 5% by mass, more preferably 0.001% by mass to 5% by mass, even more preferably 0.001, based on the total mass of the polymerizable compound. Mass %~1% by mass.

[(F) organic solvent]

The colored photosensitive composition of the present invention preferably contains (F) an organic solvent.

Further, the dispersion composition of the present invention preferably contains (F) an 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 types, and the organic solvent contained in the dispersion composition and the organic solvent contained in the colored photosensitive composition may be One type may be used in two or more types.

(F) The organic solvent is not particularly limited as long as it is a solvent which satisfies the solubility of each component and the coating property when the coloring photosensitive composition is formed, and is particularly preferably considered to dissolve the solid component. Choose from sex, coatability and safety.

Examples of the (F) organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, and butyric acid. Propyl ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, oxyacetic acid) Butyl ester (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3- Alkyl oxypropionates, alkyl 2-oxopropionates, methyl 2-oxo-2-methylpropanoate, ethyl 2-oxo-2-methylpropionate, methyl pyruvate, acetone Ethyl acetate, propyl pyruvate, methyl ethyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutyrate, and the like.

Further, examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and Ethylene glycol monomethyl ether, diethylene 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 , propylene glycol monopropyl ether acetate, and the like.

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

Examples of the aromatic hydrocarbons include toluene, xylene, and the like.

The organic solvent is preferably two in terms of the solubility of each of the above components, the solubility of the alkali-soluble binder in the case of containing an alkali-soluble binder, and the improvement of the coating surface. Mix above. In this case, it is particularly preferable to contain a mixed solution of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve acetate. Ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol Acid ester, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The content of the organic solvent in the coloring photosensitive composition is preferably a coloring feeling The total solid content concentration in the optical composition is from 10% by mass to 80% by mass, more preferably from 15% by mass to 60% by mass.

(surfactant)

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

As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant can be used, and a preferred surfactant is a nonionic surfactant. Specifically, a nonionic surfactant described in paragraph 0057 of JP-A-2009-098616 is preferable, and among them, a fluorine-based surfactant is preferable.

Other surfactants which can be used in the present invention are, for example, commercially available products, namely, Megafac F142D, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac. F781, Megafac F781-F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R-90 (manufactured by DIC), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG 7105, Asahi Guard AG 7000, Asahi Guard AG 950, Asahi Guard AG 7600, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (above manufactured by Asahi Glass Co., Ltd.), Eftop EF 351, Eftop EF 352, Eftop EF 801, Eftop EF 802 (above manufactured by Mitsubishi Materials Electronics Co., Ltd.), Ftergent 250 (manufactured by Neos).

Further, the surfactant is preferably a copolymer comprising the structural unit A and the structural unit B represented by the following formula (W), and using tetrahydrofuran as a solvent, by gel permeation chromatography. The measured polystyrene-equivalent weight average molecular weight (Mw) is 1,000 or more and 10,000 or less.

(In the formula (W), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴ represents a hydrogen atom or a carbon number of 1 or more and 4 or less. The alkyl group, L represents an alkylene group having a carbon number of 3 or more and 6 or less, p and q are mass percentages indicating a polymerization ratio, p is a numerical value of 10% by mass or more and 80% by mass or less, and q is 20% by mass or more and 90% by mass or less. In the following numerical values, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.)

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

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 above copolymer is more preferably 1,500 or more and 5,000 or less.

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

In the total solid content of the coloring photosensitive composition, the amount of the surfactant added to the coloring photosensitive composition of the present invention is preferably 0.01% by mass to 2.0% by mass, particularly preferably 0.02% by mass to 1.0% by mass. When it is this range, the coatability and the uniformity of a cured film become favorable.

(close contact improver)

The colored photosensitive composition of the present invention may contain a adhesion improving agent.

The adhesion improving agent is a compound which improves the adhesion between the inorganic substance serving as the support and the cured film of the colored photosensitive composition layer, and the inorganic substance is, for example, a bismuth compound such as glass, ruthenium, iridium oxide or tantalum nitride, gold, copper, aluminum, or the like. . Specific examples thereof include a decane coupling agent and the like. The decane coupling agent as the adhesion improving agent is not particularly limited as long as it is modified by the interface, and a known compound can be used.

The decane coupling agent is preferably a decane coupling agent described in paragraph 0048 of JP-A-2009-98616, wherein more preferably γ-glycidoxypropyltrialkoxydecane or γ-methylpropene oxime Oxypropyl propyl alkoxy decane. These compounds may be used alone or in combination of two or more.

The content of the adhesion improving agent in the coloring photosensitive composition of the present invention is preferably from 0.1% by mass to 20% by mass, and more preferably from 0.2% by mass to 5% by mass, based on the total solid content of the coloring photosensitive composition.

(crosslinking agent)

In the colored photosensitive composition of the present invention, a crosslinking agent is used in a complementary manner, and the hardness of the colored layer obtained by curing the colored photosensitive composition can be further improved.

The crosslinking agent is not particularly limited as long as it is a crosslinking agent which can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin; and (b) a selected from a methylol group and an alkoxy group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent of a methyl group and a decyloxymethyl group; (c) selected from a methylol group, an alkoxy group A phenol compound, a naphthol compound or a hydroxyquinone compound substituted with at least one substituent of a methyl group and a methoxymethyl group. Among them, a polyfunctional epoxy resin is preferred.

For details of specific examples of the crosslinking agent, etc., the descriptions of paragraphs [0134] to [0147] of JP-A-2004-295116 can be referred to.

(development accelerator)

The alkali solubility in the non-exposed region when the coloring photosensitive composition layer is exposed is promoted, and the developability of the colored photosensitive composition is further improved. In addition, a development accelerator may also be added. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1,000 or less and a low molecular weight phenol compound having a molecular weight of 1,000 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, diethyl acetic acid, heptanoic acid, and caprylic acid; and oxalic acid and propylene glycol; Acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, trisallic acid, methylmalonic acid, ethylpropane Aliphatic dicarboxylic acid such as acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, citraconic acid; 1,2,3-propane tricarboxylic acid (tricarballylic acid), aconitic acid (aconic acid) Acid), aliphatic tricarboxylic acid such as camphoronic acid; benzoic acid, toluic acid, cumic acid, 2,3-dimethylbenzoic acid, 3 , an aromatic monocarboxylic acid such as 5-dimethylbenzoic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid , 1,2,3,5-benzenetetracarboxylic acid (mellophanic acid), pyromellitic acid and other aromatic polycarboxylic acids; phenylacetic acid, hydrogenated hydratropic acid, hydrogen Hydrocinnamic acid, mandelic acid, phenyl succinic acid, atopic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumarin Coumaric acid, umbellic acid, and the like.

(other additives)

In the colored photosensitive composition of the present invention, each of the photosensitive compositions can be formulated as needed. Examples of the additive include a filler, a polymer compound other than the above, an ultraviolet absorber, and an antioxidant. Examples of the additives include the additives described in paragraphs [0155] to [0156] of JP-A-2004-295116.

The coloring photosensitive composition of the present invention may contain the light stabilizer described in paragraph [0078] of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph [0081] of the publication.

(Preparation method of coloring photosensitive composition)

The colored photosensitive composition of the present invention is prepared by mixing the above components with optional optional components. It is preferred to prepare the above components by mixing them with any optional components as necessary by using the above-mentioned dispersion composition as a colorant component.

Further, when the coloring photosensitive composition is prepared, the components constituting the colored photosensitive composition may be formulated in a total amount, or may be formulated one by one. In addition, the order of input or the working conditions at the time of preparation are not particularly restricted.

The colored photosensitive composition prepared as described above is preferably used by being filtered and separated using a filter having a pore diameter of about 0.01 μm to 3.0 μm.

The colored photosensitive composition of the present invention can form a colored cured film having excellent heat resistance and excellent contrast, and therefore can be suitably used for forming a colored pixel such as a color filter used in a liquid crystal display device, and can be suitably used for printing. Production of inks, inkjet inks, and coatings.

"Color filter and its manufacturing method"

The color filter of the present invention is provided with a support body and is provided on the support body The coloring region including the colored photosensitive composition of the present invention is provided. The colored region on the support includes colored layers such as red (R), green (G), and blue (B) which form respective pixels of the color filter.

The method for producing a color filter of the present invention comprises the steps of: a colored layer forming step (A), applying the colored photosensitive composition onto a support to form a colored layer (colored photosensitive composition layer); and exposing Step (B), performing patterning exposure on the coloring layer formed by the step (A); and developing step (C), developing the exposed coloring layer to form a colored pattern.

Further, in the method of producing a color filter of the present invention, it is particularly preferable to further provide an embodiment of the step (D) of heat-treating the colored pattern obtained in the step (C).

Hereinafter, a method of producing the color filter of the present invention will be described more specifically.

-Step (A)-

In the method for producing a color filter of the present invention, first, coating is applied to a support by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, or inkjet. The colored photosensitive composition of the present invention forms a colored layer, and then the colored layer is dried by heating (prebake) or vacuum drying.

Examples of the support include soda glass, alkali-free glass, borosilicate glass, quartz glass, a ruthenium substrate, and a resin substrate used in a liquid crystal display device. Further, on these supports, an undercoat layer may be provided in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface as needed.

The pre-baking conditions may be, for example, heating at 70 ° C to 130 ° C for 0.5 minutes to 15 minutes using a hot plate or an oven.

Further, the thickness of the coloring layer formed by the coloring photosensitive composition is appropriately selected depending on the purpose. The color filter for a liquid crystal display device preferably has a range of 0.2 μm to 5.0 μm, and more preferably 1.0 μm to 4.0 μm. Further, the thickness of the colored layer is the film thickness after drying.

-Step (B)-

Then, in the method of producing a color filter of the present invention, the coloring layer formed on the support is subjected to pattern pattern exposure. The light or radiation that can be applied to the exposure is preferably a g-line, an h-line, an i-line, or various kinds of laser light, and particularly preferably an i-line. In the case where a high pressure mercury lamp is used for the irradiation of light, it is preferably irradiated with an exposure amount of 5 mJ/cm ² to 500 mJ/cm ² .

In addition, other exposure light sources can be used: ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps. Lamp), various laser light sources, etc.

~ Exposure step using a laser source~

In the exposure mode using a laser light source, the illumination light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 410 nm, and particularly preferably a wavelength in the range of 300 nm to 360 nm. In particular, it is particularly suitable to use a third harmonic (355 nm) of a neon-doped yttrium aluminum garnet (Nd:YAG) laser of a solid laser which is relatively expensive and relatively inexpensive, or Excimer laser XeCl (308 nm), XeF (353 nm). The pattern exposure amount is preferably in the range of 1 mJ/cm ² to 100 mJ/cm ² from the viewpoint of productivity, and more preferably in the range of 1 mJ/cm ² to 50 mJ/cm ² .

The exposure apparatus is not particularly limited, and a commercially available exposure apparatus can be used by Callisto (manufactured by V-Technology Co., Ltd.), EGIS (manufactured by V Technology Co., Ltd.), or DF2200G (manufactured by Dainippon Wire Mesh Co., Ltd.). Wait. Further, devices other than the above may be suitably used.

-Step (C)-

Then, the exposed coloring layer is developed using a developing solution. Thereby, a colored pattern can be formed. The developer may be a combination of a plurality of organic solvents or an alkaline aqueous solution as long as it dissolves the uncured portion of the colored layer and does not dissolve the developer of the cured portion. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted so that the pH is 10 to 13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, and tetramethyl. Ammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7-undecene (1,8-diazabicyclo -[5,4,0]-7-undecene) and other alkaline aqueous solutions.

The development time is preferably from 30 seconds to 300 seconds, and particularly preferably from 30 seconds to 120 seconds. The developing temperature is preferably from 20 ° C to 40 ° C, particularly preferably 23 ° C.

The development can be carried out by a puddle method, a shower method, a spray method, or the like.

Further, after development using an aqueous alkaline solution, it is preferably washed with water.

In the method for producing a color filter of the present invention, it is particularly preferable to perform post-exposure by ultraviolet irradiation on a coloring pattern (pixel) formed using a coloring photosensitive composition.

-Step (D)-

It is preferable to further heat-treat the colored pattern after development or the colored pattern which has been subjected to post-exposure by ultraviolet irradiation as described above. The colored pattern can be further hardened by heat-treating the formed colored pattern (so-called post-baking treatment). This heat treatment can be performed, for example, using a hot plate, various heaters, an oven, or the like.

The temperature during the heat treatment is preferably from 100 ° C to 300 ° C, particularly preferably from 150 ° C to 250 ° C. Further, the heating time is preferably from about 10 minutes to about 120 minutes.

The colored pattern obtained in the above manner constitutes a blue pixel in the color filter. When a color filter having a plurality of hues of pixels is produced, the above steps (A), (B), (C), and (D) may be repeated in accordance with the desired number of colors.

Further, the above step (D) may be performed every time the formation, exposure, and development of the monochromatic colored layer is completed (per color), or after the formation, exposure, and development of all the colored layers of the desired color number are completed. The above step (D) is carried out.

Further, the colored photosensitive composition of the present invention can form a blue coloring layer and set the blue pixel on the support. However, when the colored pixel includes red, blue, and green, the order of providing the colored layer may be Any order.

Display device

The color filter (the color filter of the present invention) obtained by the method for producing a color filter of the present invention is excellent in heat resistance and contrast because the coloring photosensitive composition of the present invention is used.

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

Specifically, the display device of the present invention is preferably a liquid crystal display (liquid crystal display, LCD), an organic electroluminescence (EL) display (organic EL display device), a liquid crystal projector, a game machine. A display device such as a display device, a mobile phone display device, a display device for a digital camera, or a display device for a car navigation device is particularly suitable as a color display device.

When the color filter of the present invention is used in an organic EL display device or a liquid crystal display device or the like, not only a good hue but also an image excellent in spectral characteristics and contrast can be displayed.

<Liquid crystal display device>

A liquid crystal display device using the color filter of the present invention will be described. The definition of the organic EL display device or the liquid crystal display device or the details of each display device is described, for example, in "Electronic display device (sasaki Sasaki, Ltd., issued by the Industrial Research Association in 1990)" and "display device (Ibuki Shunzhang) , Industrial Books (shares issued in 1989)" and so on. In addition, the liquid crystal display device is described in, for example, "Next-Generation Liquid Crystal Display Technology (Edited by Uchida Natsuo, Industrial Research Association, 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, various types of liquid crystal displays described in the "Next Generation Liquid Crystal Display Technology". Device.

Among them, the color filter of the present invention is particularly effective for a thin film transistor (TFT) type liquid crystal display device. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". Furthermore, the present invention is also applicable to a liquid crystal display device having a wide viewing angle such as a transverse electric field driving method such as an in-plane switching (IPS), a multi-domain vertical alignment (MVA), or the like. , or super twisted nematic (STN), twisted nematic (TN), vertical alignment (VA), optically compensated splay (OCS), fringe field switching (fringe field) Switching, FFS), and reflective optically compensated bend (R-OCB). In addition, the color filter of the present invention can also be provided to 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 achieved when combined with a three-wavelength tube of a previously known cold cathode tube, and further, by using red, green, and blue LED light sources (RGB-LED) As a backlight, it is possible to provide a liquid crystal display device having high luminance and high color reproducibility.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but it is not limited to the following examples. In addition, "%" and "parts" are quality standards unless otherwise specified.

[Example 1] - Preparation of blue dispersion composition 1 - <Preparation of Composition of Colored Materials>

100 parts of commercially available CI Pigment Blue 15:6 (product name: DIC Co., Ltd., FASTGEN BLUE EP193), 50 parts of dye (exemplified compound 1 of the above dye), 400 parts of sodium chloride, and a water-soluble organic solvent 140 parts of diethylene glycol was added to a table type kneading machine (manufactured by the Chamber of Commerce), and kneaded for 10 hours. Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain a colored material composition of C.I. Pigment Blue 15:6 and a dye.

Rough dispersion

After the above-mentioned colored material composition was blended with the following composition, the mixture was dispersed using Eiger-mill (manufactured by Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.8 mm.

. Colored material composition: 150 parts

. Pigment derivative (I) (structure described below): 10 parts

. Polymer dispersant (exemplified compound 1 below): 80 parts

. Propylene glycol monomethyl ether acetate: 260 parts

Further, the pigment derivative (I) is synthesized in accordance with the method described in paragraph 0056 of JP-A-2003-253078. CuPc in the following structural formula represents a copper phthalocyanine residue. In addition, the exemplified compound 1 is based on Japanese patents. The method described in JP-A-2011-178865 is synthesized.

<Precision dispersion>

The above-mentioned coarsely dispersed dispersion was taken out, and 30 parts of propylene glycol monomethyl ether acetate was added to 100 parts of the dispersion, and the mixture was mixed. Then, dispersion was carried out using an Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.1 mm.

<concentration adjustment>

Take out the precisely dispersed dispersion in a way that the pigment concentration reaches 10% Dilute to propylene glycol monomethyl ether acetate to prepare a blue dispersion composition 1.

- Preparation of coloring photosensitive composition -

The coloring photosensitive composition 1 was prepared by mixing and dissolving each component mentioned below.

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

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

. Alkali-soluble binder 1: methacrylic acid cyclohexyl methacrylate / methacrylic acid / glycidyl methacrylate (= molar ratio: 30/30/40) methacrylic acid adduct (45% propylene glycol monomethyl Ether solution) 4 parts

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

. Polymeric Compound 1: Manufactured by Nippon Chemical Co., Ltd., KAYARAD DPHA 3 parts

. Polymeric Compound 2: East Asian Synthetic (Stock), Aronix TO-2349 3 parts

. Polymerization inhibitor: p-methoxyphenol 0.003 parts

. Photopolymerization initiator: 1-(O-ethylindenyl)-1-[9-ethyl-6-(thiophenylhydrazinyl)-9H-indazol-3-yl]acetone 0.3 parts

. Photopolymerization initiator 2: 1,3-dihydro-1-phenyl-2H-benzimidazole-2-thione 0.2 parts

. Polyfunctional thiol compound: 1,4-bis(3-mercaptobutoxy)butane 0.1 part

. Adhesion improver: 3-methacryloxypropyltrimethoxydecane 0.2 parts

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

. Blue dispersion composition 1 30 parts

[Example 2 to Example 6]

In the first embodiment, the colored photosensitive composition 2 to the colored photosensitive composition 6 were produced in the same manner as in Example 1 except that the dye used in the preparation of the colored material composition was changed to the one shown in Table 1.

[Embodiment 7] - Preparation of blue dispersion composition 7 - <Micronization of Pigments>

100 parts of the commercially available CI Pigment Blue 15:6, 400 parts of sodium chloride, and 140 parts of diethylene glycol used in Example 1 were added to a table type kneader (manufactured by Jiangshang Chamber of Commerce). Mix for 10 hours. Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain a fine pigment of C.I. Pigment Blue 15:6.

Rough dispersion

After the above-mentioned finely divided pigment was blended with the following composition, the mixture was dispersed using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.8 mm.

. Micronized pigment 100 parts

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

. Pigment derivative (I) 10 parts

. Polymer dispersant: exemplified compound 1 80 parts

. Propylene glycol monomethyl ether acetate: 40 parts

<Precision dispersion>

The above-mentioned coarsely dispersed dispersion was taken out, and then dispersed using an Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.1 mm.

<concentration adjustment>

The finely dispersed dispersion was taken out and diluted with propylene glycol monomethyl ether acetate so as to have a pigment concentration of 10% to prepare a blue dispersion composition 7.

- Preparation of coloring photosensitive composition 7 -

In the first embodiment, the colored photosensitive composition 7 was produced in the same manner as in Example 1 except that the blue dispersion composition 1 was replaced with the blue dispersion composition 7.

[Example 8 to Example 12]

In the same manner as in Example 7, except that the dye added to the coarse dispersion was changed to the one shown in Table 1, the colored photosensitive composition 8 to the colored photosensitive composition 12 were produced.

[Example 13] - Preparation of blue dispersion composition 13 - <Micronization of Pigments>

100 parts of the commercially available CI Pigment Blue 15:6, 400 parts of sodium chloride, and 140 parts of diethylene glycol used in Example 1 were added to a table type kneader (manufactured by Jiangshang Chamber of Commerce). Mix for 10 hours. Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain a fine pigment of C.I. Pigment Blue 15:6.

Rough dispersion

After the above-mentioned finely divided pigment was blended with the following composition, the mixture was dispersed using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.8 mm. At this time, the fine pigment is initially mixed with the dye in a powder state, and then other materials are added to be dispersed.

. Micronized pigment 100 parts

. Dye: an exemplary compound of the dye 1 50 parts

. Pigment derivative (I) 10 parts

. Polymer dispersant: exemplified compound 1 80 parts

. Propylene glycol monomethyl ether acetate 260 parts

<Precision dispersion>

The above-mentioned coarsely dispersed dispersion was taken out, and 30 parts of propylene glycol monomethyl ether acetate was added to 100 parts of the dispersion, and the mixture was mixed. Then, dispersion was carried out using an Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.1 mm.

<concentration adjustment>

The finely dispersed dispersion composition was taken out and diluted with propylene glycol monomethyl ether acetate so as to have a pigment concentration of 10% to prepare a blue dispersion composition 13.

- Preparation of coloring photosensitive composition 13 -

In the first embodiment, the colored photosensitive composition 13 was produced in the same manner as in Example 1 except that the blue dispersion composition 1 was changed to the blue dispersion composition 13.

[Examples 14 to 18]

In the same manner as in Example 13, except that the dye added to the coarse dispersion was changed to the one shown in Table 1, the colored photosensitive composition 14 to the colored photosensitive composition 18 were produced.

[Embodiment 19] - Preparation of blue dispersion composition 19 - <Micronization of Pigments>

100 parts of the commercially available CI Pigment Blue 15:6, 400 parts of sodium chloride, and 140 parts of diethylene glycol used in Example 1 were added to a table type kneader (manufactured by Jiangshang Chamber of Commerce). Mix for 10 hours. Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain a fine pigment of C.I. Pigment Blue 15:6.

Rough dispersion

After the above-mentioned finely divided pigment was blended with the following composition, the mixture was dispersed using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.8 mm.

. Micronized pigment 100 parts

. Pigment derivative (I) 10 parts

. Polymer dispersant: exemplified compound 1 80 parts

. Propylene glycol monomethyl ether acetate 260 parts

<Precision dispersion>

The above-mentioned crude dispersion dispersion was taken out, and 11 parts of the dyed exemplary compound 1 was further added to 100 parts of the dispersion, and mixed. Then, 30 parts of propylene glycol monomethyl ether acetate was added, and dispersion was carried out using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.1 mm.

<concentration adjustment>

The finely dispersed dispersion composition was taken out and diluted with propylene glycol monomethyl ether acetate so as to have a pigment concentration of 10% to prepare a blue dispersion composition 19.

- Preparation of coloring photosensitive composition 19 -

In the first embodiment, the colored photosensitive composition 19 was produced in the same manner as in Example 1 except that the blue dispersion composition 1 was changed to the blue dispersion composition 19.

[Example 20 to Example 24]

In the same manner as in Example 19 except that the dye added during the fine dispersion was changed to the one shown in Table 1, the colored photosensitive composition 20 to the colored photosensitive composition 24 were produced.

[Comparative Example 1] - Preparation of blue dispersion composition A - <Micronization of Pigments>

100 parts of the commercially available CI Pigment Blue 15:6, 400 parts of sodium chloride, and 140 parts of diethylene glycol used in Example 1 were added to a table type kneader (manufactured by Jiangshang Chamber of Commerce). Mix for 10 hours. Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain a fine pigment of C.I. Pigment Blue 15:6.

Rough dispersion

After the above-mentioned finely divided pigment was blended with the following composition, the mixture was dispersed using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.8 mm.

. Micronized pigment 100 parts

. Pigment derivative (I) 10 parts

. Polymer dispersant: exemplified compound 1 80 parts

. Propylene glycol monomethyl ether acetate 260 parts

<Precision dispersion>

The above-mentioned coarsely dispersed dispersion was taken out, and 100 parts of the dispersion was mixed with 125 parts of the exemplified compound 1 (9% solution of propylene glycol monomethyl ether acetate) of the dye. Then, dispersion was carried out using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.1 mm to obtain a blue dispersion composition A having a pigment concentration of 10%.

- Preparation of coloring photosensitive composition A -

In the first embodiment, the colored photosensitive composition A was produced in the same manner as in Example 1 except that the blue dispersion composition 1 was changed to the blue dispersion composition A.

[Comparative Example 2] - Preparation of blue dispersion composition B - <Micronization of Pigments>

100 parts of the commercially available CI Pigment Blue 15:6, 400 parts of sodium chloride, and 140 parts of diethylene glycol used in Example 1 were added to a table type kneader (manufactured by Jiangshang Chamber of Commerce). Mix for 10 hours. Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain C.I. Pigment Blue 15:6.

Rough dispersion

After the above-mentioned finely divided pigment was blended with the following composition, the mixture was dispersed using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.8 mm.

. Micronized pigment 100 parts

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

. Polymer dispersant (exemplified compound A) 80 parts

. Propylene glycol monomethyl ether acetate 260 parts

<Precision dispersion>

The above-mentioned coarsely dispersed dispersion was taken out, and 19 parts of propylene glycol monomethyl ether acetate was added to 100 parts of the dispersion, followed by mixing. Then, dispersion was carried out using an Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.1 mm. After the dispersion, 11 parts of a dye (exemplified compound 1 of the dye) was added, and the mixture was mixed by a Three-One Motor to obtain a blue dispersion composition B.

- Preparation of coloring photosensitive composition B -

In the first embodiment, the colored photosensitive composition B was produced in the same manner as in Example 1 except that the blue dispersion composition 1 was changed to the blue dispersion composition B.

[Comparative Example 3] - Preparation of blue dispersion composition C -

After blending with the following composition, the mixture was dispersed using a paint shaker (manufactured by Seiwa Giken) and zirconia beads having a diameter of 0.1 mm to obtain a blue dispersion composition C.

. Commercially available C.I. Pigment Blue 15: 6 100 parts used in Example 1.

. Exemplary compound of the dye 1 50 parts

. Pigment derivative (I) 10 parts

. Polymer dispersant (exemplified compound 1) 80 parts

. Propylene glycol monomethyl ether acetate 760 parts

- Preparation of coloring photosensitive composition C -

In the first embodiment, the colored photosensitive composition C was produced in the same manner as in Example 1 except that the blue dispersion composition 1 was changed to the blue dispersion composition C.

The Ci and Cf in the coloring photosensitive composition produced in the above manner are as follows.

The Ci in Examples 1 to 6 was calculated based on the concentration of the specific dye at the time of premixing, and both were 33.3%; and Cf was calculated from the concentration of the dye in the dispersion composition after the concentration after the completion of the dispersion. In each of Examples 1 to 6, it was 5.0%.

Further, Ci in Examples 7 to 18 was calculated based on the composition of the coarse dispersion. The Ci of Examples 7 to 12 were both 5.5%, and the Ci of Examples 13 to 18 were both 10%. Cf is calculated from the concentration of the dye in the dispersion composition after the concentration after the completion of the dispersion, and is 5.0% in each of Examples 7 to 18.

In Examples 19 to 24, Ci was calculated based on the composition of the fine dispersion, and both were 7.8%; Cf was calculated based on the concentration of the dye in the dispersion composition after the concentration at the end of the dispersion, and both were 5.0%. .

Further, Comparative Example 1 to Comparative Example 3 were all Ci=Cf and both were 5.0%.

-Evaluation-

As a performance evaluation of the colored photosensitive composition 1 to the colored photosensitive composition 24 and the colored photosensitive composition A to the colored photosensitive composition C, the spectral characteristics, contrast, and heat resistance were measured by the following methods. Evaluation. Further, the dye adsorption ratio to the pigment in each of the blue dispersion compositions was also evaluated. The evaluation results are shown in Table 1 below.

- Formation of a coloring photosensitive composition layer (colored layer) -

The colored photosensitive composition prepared above was applied onto a glass (#1737; manufactured by Dow Corning) substrate by a spin coating method, and then dried at room temperature for 30 minutes to volatilize volatile components. The color layer is formed. The colored layer was irradiated with an i-line (wavelength of 365 nm) through a mask of a thin line pattern to form a latent image. The light source of the i-line is an ultra-high pressure mercury lamp, which is formed by parallel light and then irradiated. At this time, the amount of irradiation light was set to 40 mJ/cm ² . Then, the coloring layer on which the latent image was formed was developed using an aqueous solution of sodium carbonate/sodium hydrogencarbonate (concentration: 2.4%) at 26 ° C for 45 seconds, followed by rinsing with running water for 20 seconds, and then dried by spraying. , get a thin line pattern image. The obtained fine line pattern image was subjected to post-baking treatment at 230 ° C for 20 minutes to obtain a colored layer having a blue fine line pattern having a film thickness of 2 μm.

(contrast evaluation)

The substrate having the obtained colored layer was sandwiched between two polarizing films, and a color luminance meter (manufactured by Topcon Co., model: BM-5A) was used to measure the polarization axes of the two polarizing films in parallel and perpendicularly. The value of the brightness at the time, the brightness when the polarization axes of the two polarizing films are parallel is divided by the brightness at the vertical, and the obtained value is obtained as a comparison. degree. The higher the contrast, the better the performance as a color filter for a liquid crystal display device.

(Spectral characteristics)

The transmission spectrum of the coloring layer obtained above was measured using a microscopic spectrometry apparatus (manufactured by Olympus Co., Ltd., model OSP-SP200). Based on the obtained breakthrough spectrum, the chromaticity coordinates x, y, and Y values in the CIE 1931 color specification system are obtained.

The spectral characteristic can be said that the larger the Y value in (x, y) = (0.138, 0.085), the more excellent the spectral characteristics.

(heat resistance)

The transmission spectrum of the obtained colored layer was measured using a microscopic spectrometry apparatus (manufactured by Olympus Co., Ltd., model OSP-SP200), and then baked at 230 ° C for 60 minutes to re-evaluate the breakthrough spectrum. The Y value difference (ΔY) before and after the additional baking was calculated, and this was used as an index of heat resistance. The smaller the ΔY, the more excellent the heat resistance.

(dye adsorption rate)

Each blue dispersion composition was centrifuged at 50,000 rpm by an ultracentrifuge (manufactured by Hitachi Koki Co., Ltd.) to obtain a supernatant containing a free component. In addition, the ultracentrifuge used in the above-mentioned centrifugation is set to CS150GX (manufactured by Hitachi Ltd.), the centrifugal capacity is 1 g, and the centrifugation time (may vary depending on the sample) is usually 1 hour to 6 hours. about. The amount of the dye in the supernatant was evaluated by HPLC, and the adsorption ratio (%) was defined by the following formula.

From the results of Table 1, the following can be seen. The coloring photosensitive composition of the present invention is colored with respect to the coloring photosensitive composition A to the coloring photosensitive composition C of the comparative example. The coloring photosensitive composition 24 has excellent heat resistance. The heat resistance is related to the dye adsorption rate, and therefore it is presumed that thermal fading is suppressed by adsorbing the dye on the pigment. Since the dispersion composition of the present invention has a high dye adsorption rate, it is easy to obtain high heat resistance.

The reason for this is considered to be that the dye concentration Ci when the dye is introduced is higher than the dye concentration Cf in the final dispersion composition in the preparation of the dispersion composition of the present invention. In other words, it is considered that adsorption of the pigment is easily caused by inputting the dye at a higher concentration (for example, when the dye is added in a solid state when the pigment described in Example 1 is refined).

As shown in the comparative example, even when the dye was added to the dispersion step at a low concentration (Comparative Example 1), the mixture was simply stirred and mixed after the dispersion step (Comparative Example 2), and dispersed. Insufficient, when the pigment is not sufficiently broken and the particle surface area is small (Comparative Example 3), the dye adsorption rate is low, and thus the heat resistance is also lowered.

In addition, the colored photosensitive composition 1 to the colored photosensitive composition 24 of the present invention have an excellent contrast ratio compared with the colored photosensitive composition A to the colored photosensitive composition C of the comparative example. The reason for this is not sufficiently clear, but it is considered that the reason is that since the dye is adsorbed on the surface of the pigment, the amount of free dye in the dispersion composition is small, so that aggregation of the dye during formation of the colored layer is suppressed. It is presumed that the aggregation of the dye is suppressed, and the particles in the coloring layer which causes light scattering are reduced, so that the contrast is improved.

[Example 25] <Production of Liquid Crystal Display Device>

A color filter was produced by the following method, and liquid crystal display devices LCD-B1 to LCD-B14 using the color filter were produced, and display characteristics were evaluated.

<Preparation of Red Colored Photosensitive Composition R>

The following red pigment dispersion compositions were mixed and stirred using a homogenizer at 3,000 rpm for 3 hours. Further, the mixed solution obtained in the above manner was subjected to dispersion treatment for 12 hours by a bead disperser Dispermat (manufactured by GETZMANN) using 0.3 mm φ zirconia beads, and then, a high pressure dispersing machine with a pressure reducing mechanism was further used. NANO-3000-10 (manufactured by BEE Co., Ltd.) was subjected to dispersion treatment at 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 75 parts

. C.I. Pigment Red 177 50 parts

. Benzyl methacrylate/methacrylic acid copolymer 70 parts (copolymerization composition ratio 70/30, weight average molecular weight 30,000, acid value 40)

. Propylene glycol monomethyl ether acetate 800 parts

Further, a component having the following composition was further added to the obtained pigment dispersion to prepare a red colored photosensitive composition R.

[Red coloring photosensitive composition R composition]

. The above red pigment dispersion 100 parts

. Benzyl methacrylate/methacrylic acid (=70/30 [mole ratio]) copolymer (Mw: 30,000) propylene glycol monomethyl ether acetate solution (solid content 50%) 12 copies

. Polymeric Compound 1: Made by Nippon Chemical Co., Ltd., KAYARAD DPHA 12.1

. Photopolymerization initiator: 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer 3.1 parts

. Sensitizing pigment: 4,4'-bis(diethylamino)benzophenone 4.2 parts

. Hydrogen-donating compound: 2-mercaptobenzothiazole 2.1 parts

. Polymerization inhibitor: p-methoxyphenol 0.001 parts

. Fluorine-based surfactant (trade name: manufactured by Megafac R08 DIC) 0.5 parts

. Propylene glycol monomethyl ether acetate 60 parts

<Preparation of Green Coloring Photosensitive Composition G>

In the preparation of the red colored photosensitive composition R, 103 parts of CI Pigment Green 58 were used instead of CI Pigment Red 254, and 19 parts of CI Pigment Yellow 150 were used instead of CI Pigment Red 177, and the same method was used. Green coloring photosensitive composition G.

<Production of Black Coloring Photosensitive Composition K>

The pigment dispersion composition having the following composition was changed, and dispersion treatment was carried out in the same manner as in the preparation of the red pigment dispersion to prepare a black pigment dispersion.

[Black pigment dispersion composition]

. Carbon black: Trade name: Nipex35, Made in Japan Degussa Japan (shares) 13.1 copies

. Polymer: benzyl methacrylate / methacrylic acid = 72/28 molar ratio of random copolymer (molecular weight of 37,000) 6.7 parts

. Propylene glycol monomethyl ether acetate 79.1 parts

. Dispersing agent (the following compound) 0.65 parts

Using the obtained black pigment dispersion composition, the black coloring photosensitive composition K was adjusted in the following composition.

[Black coloring photosensitive composition K composition]

. The above black pigment dispersion 25 parts

. Propylene glycol monomethyl ether acetate 8.5 parts

. Methyl ethyl ketone 53 parts

. Polymer: benzyl methacrylate/methacrylic acid = 78/22 molar ratio random copolymer (molecular weight: 38,000) mixture of 27 parts and propylene glycol monomethyl ether acetate 73 parts 9.1 parts

. Polymerization inhibitor: hydroquinone monomethyl ether 0.002 parts

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

. Polymerization initiator: 2,4-bis(trichloroethyl)-6-[4'(N,N-diethoxycarbonylmethyl)amino-3'-bromophenyl]-s-triazine 0.16 Share

. Methyl ethyl ketone 30% solution of surfactant (the following compound) 0.042 parts

(n=6, x=55, y=5, Mw=33940, Mw/Mn=2.55 PO: propylene oxide, EO: ethylene oxide)

<Production of Color Filters> <Formation of Black Matrix>

After cleaning the alkali-free glass substrate with an ultraviolet (UV) cleaning device, it is brushed with a cleaning agent, and ultrasonic cleaning is performed with ultrapure water. The substrate was heat-treated at 120 ° C for 3 minutes to stabilize the surface state, and then the substrate was cooled and adjusted to 23 ° C.

On the substrate, a glass substrate coating machine (manufactured by FAS Asia, trade name: MH-1600) having a slit nozzle was used for coating. The black colored photosensitive resin composition K is described. Then, using VCD (Vacuum Drying Apparatus, manufactured by Tokyo Ohka Kogyo Co., Ltd.), a part of the solvent was dried in 30 seconds to eliminate the fluidity of the coating layer, and then prebaked at 120 ° C for 3 minutes to obtain a film thickness. It is a 2.4 μm black photosensitive composition layer.

A state in which a substrate and a mask (a quartz exposure mask having an image pattern) are vertically erected by a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp Next, the distance between the exposure mask surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ/cm ² .

Then, the pure water is sprayed by a shower nozzle to uniformly wet the surface of the black photosensitive composition layer, and then a KOH-based developing solution (containing KOH, a nonionic surfactant, trade name: CDK-1, Fujifilm) is used. The electronic material (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was spray-developed under the conditions of 23 ° C, 80 seconds, and a flat nozzle pressure of 0.04 MPa to obtain a patterned image. Then, ultra-pure water was sprayed at a pressure of 9.8 MPa using an ultra-high pressure washing nozzle to carry out residue removal. Finally, heat treatment was carried out at 220 ° C for 30 minutes to form a black matrix.

<Formation of RGB pixels>

On the glass substrate on which the black matrix was formed, the red colored photosensitive composition R, the green colored photosensitive composition G, and the blue photosensitive composition prepared in Example 1 were formed in the same procedure as in the case of forming the black matrix. The layers are sequentially layered and patterned to obtain color filters of RGB 3 color pixels. At this time, the thickness of the coloring portion of each of the RGB colors was 1.6 μm.

<Formation of Indium Tin Oxide (ITO) Electrode>

The glass substrate on which the color filter was formed was placed in a sputtering apparatus, and 1300 Å thick ITO was vacuum-deposited at 100 ° C, and then annealed at 240 ° C for 90 minutes to crystallize ITO to form ITO transparent. electrode.

<Formation of spacers>

A spacer is formed on the ITO transparent electrode produced as described above in the same manner as the method of forming a spacer described in [Example 1] of JP-A-2004-240335.

<Formation of protrusions for liquid crystal alignment control>

A liquid crystal alignment control projection is formed on the ITO transparent electrode on which the separator is formed by using the following coating liquid for a positive photosensitive resin layer.

Among them, the exposure, development, and baking steps use the following methods.

A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) was placed so as to have a distance of 100 μm from the surface of the photosensitive resin layer in a predetermined mask, and the irradiation energy was 150 mJ by using an ultrahigh pressure mercury lamp through the mask. /cm ² performs proximity exposure.

Then, while developing the substrate by spraying a 2.38% tetramethylammonium hydroxide aqueous solution at 33 ° C for 30 seconds by a shower type developing device. By developing and removing the unnecessary portion (exposure portion) of the photosensitive resin layer, a substrate for a liquid crystal display device in which a liquid crystal alignment control projection is formed on the color filter side substrate, the liquid crystal alignment control projection is obtained. A photosensitive resin layer patterned into a desired shape is included.

Then, the substrate for a liquid crystal display device in which the liquid crystal alignment control projections were formed was baked at 230 ° C for 30 minutes to form a cured liquid crystal alignment control projection on the liquid crystal display device substrate.

[Formulation of Coating Solution for Positive Photosensitive Resin Layer]

. Positive resist liquid (manufactured by Fujifilm Electronic Materials Co., Ltd., FH-2413F) 53.0 parts

. Methyl ethyl ketone 46.5 parts

. Megafac F-780F (manufactured by DIC) 0.05 parts

<Production of Liquid Crystal Display Device>

Further, an alignment film containing polyimine is further provided on the substrate for a liquid crystal display device obtained above. Then, the sealant of the epoxy resin is printed at a position corresponding to the pixel matrix surrounding the color filter so as to be placed around the surrounding black matrix frame, and the MVA mode liquid crystal is dropped, and the counter substrate is bonded. The bonded substrate is subjected to heat treatment to harden the sealant.

On both sides of the liquid crystal cell obtained in the above manner, a polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached. Then, an LED light source (a liquid crystal television manufactured by Sony Corporation, a backlight source of KDL-40ZX1) is disposed as a light source on the side of the liquid crystal cell on which the polarizing plate is provided, and is formed as a liquid crystal display device (LCD). ).

The liquid crystal display device produced in the above manner has high contrast and brightness and is suitable as a display device. In addition, in the present embodiment, the evaluation of the MVA mode liquid crystal display device was performed, but it is considered that the liquid crystal display device in other modes may have In the color filter of the EL (Organic Electro-Luminescence) display, the coloring photosensitive composition of the present invention is used, and good image quality is also obtained.

Claims (13)

A colored photosensitive composition comprising: (A) a blue pigment, (B) a dye having a parent skeleton different from the above blue pigment, and (C) a polymerizable compound, and 15% by mass of the above (B) dye The above is adsorbed on the surface of the above (A) blue pigment. The colored photosensitive composition according to claim 1, which comprises a dispersion composition obtained by dispersing the (A) blue pigment and the (B) dye in the same system. The coloring photosensitive composition according to the second aspect of the invention, wherein the dispersion composition is a dispersion of the dye (B) in the dispersion composition at the initial stage of dispersion, and is dispersed after the dispersion is completed. When the concentration of the above (B) dye in the composition is Cf, the dispersion composition satisfying the relationship of Ci>Cf. The color-sensitive photosensitive composition according to claim 1, wherein the (B) dye is a metal complex compound having a structure represented by the following formula (I) and which is bonded to a metal atom or a metal compound: In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, or an aromatic group. A group or a heterocyclic group. The colored photosensitive composition according to claim 1, comprising: a dispersion composition obtained by preliminarily mixing the (A) blue pigment with the (B) dye, and dispersing the obtained colored material mixture. . The colored photosensitive composition according to claim 1, which further comprises (D) a photopolymerization initiator. The colored photosensitive composition according to claim 1, further comprising (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 method of producing a color filter, comprising: a colored layer forming step of applying a colored photosensitive composition according to any one of claims 1 to 7 to a support to form a colored layer And an exposing step of exposing the formed coloring layer to a pattern pattern; and developing a step of developing the exposed coloring layer to form a colored pattern. A display device comprising the color filter of claim 8 of the patent application. A display device comprising a color filter obtained by the manufacturing method as described in claim 9 of the patent application. A method for producing a colored photosensitive composition, which comprises (A) a blue pigment and (B) a dye having a parent skeleton different from the blue pigment described above, and is prepared by dispersing a dye The composition was dispersed, and then the above-mentioned dispersion composition was used to prepare a colored photosensitive composition. A method for producing a colored photosensitive composition, wherein (A) a blue pigment and (B) a dye having a parent skeleton different from the blue pigment are mixed to prepare a colored material composition, and the colored material composition is used The dispersion was prepared to prepare a dispersion composition, and then the above dispersion composition was used to prepare a colored photosensitive composition.