JP5759923B2 - Colored photosensitive composition, color filter, method for producing the same, and display device - Google Patents

Description

  The present invention relates to a colored photosensitive composition, a color filter, a method for producing the same, and a display device.

A pigment dispersion method is known as one of methods for preparing a colored photosensitive composition used for producing a color filter used in a liquid crystal display device or a solid-state imaging device (CCD, CMOS, etc.).
This pigment dispersion method is a method for producing a color filter by a photolithography method using a colored photosensitive composition in which a pigment is dispersed in various photosensitive compositions. This is a method suitable for producing a color filter with high positional accuracy, a large screen, and high definition because patterning is performed by a photolithography method. When producing a color filter 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 a colored pattern is formed by exposing and developing the coating film. A color filter is obtained by repeating the operation for each color. As the colored photosensitive composition, for example, a blue colored photosensitive composition for a color filter containing a phthalocyanine pigment is known (for example, see Patent Document 1).

In recent years, performance requirements for color filters have become stricter, with particular emphasis on hue and brightness.
Corresponding to such a situation, a technique of using a dye instead of a pigment has been conventionally proposed (see, for example, Patent Documents 1 to 3). However, dyes are generally known to be inferior in heat resistance compared to pigments, and further improvements are required in order to fully exhibit the dye performance.
For this reason, a technique of using a dye and a pigment in combination has also been developed. For example, water-based ink jet recording inks using pigments adsorbed with dyes have been proposed (see, for example, Patent Documents 4 and 5), but they are not resistant to color filter applications and further technical development is desired. It is rare. It has also been proposed to disperse a pigment with a polymer dispersant to form a dispersion composition containing a dye that is not adsorbed on the surface of the pigment, and to provide a colored photosensitive composition using this dispersion composition. (For example, see Patent Document 6.)

Japanese Patent No. 3387541 JP 2008-292970 A JP 2009-86375 A Japanese Patent Laid-Open No. 9-151344 Japanese Patent No. 4167053 JP 2011-178865 A

Further, as a method for preparing a colored photosensitive composition using a pigment and a dye, a method in which a powder dye is directly mixed in a pigment dispersion in which a pigment is dispersed can be considered. 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, the powder dye is added directly to the pigment dispersion, and the dye is dissolved in the solvent in the stirring and dissolving step after the addition. The dispersion state of the pigment changes in the process of being dissolved in the pigment, and the dispersibility and dispersion stability of the pigment tend to deteriorate.
In this method, it may take a long time to dissolve the powder dye, the dye may not be completely dissolved, or the dye may not be mixed uniformly. Furthermore, there is a concern that it is difficult to confirm that the dye has been dissolved, which hinders production.
The colored photosensitive composition obtained by these methods described above has high heat resistance and cannot sufficiently meet the demand for a color filter capable of displaying a high-quality image, and further improvement is desired. .

The present invention has been made in view of the above situation. That is, an object of the present invention is to provide a colored photosensitive composition capable of forming a colored layer having good heat resistance, high luminance, and high contrast when a colored layer such as a color filter is formed. .
The present invention also provides a color filter that uses the colored photosensitive composition and is capable of displaying an image with high brightness and high contrast, a method for producing the same, and a display with good image quality provided with the color filter. It is an object of the present invention to provide a display device capable of performing the above.

The above object of the present invention is achieved by the following means.
<1> (A) a blue pigment, and (B) a dye having a mother skeleton different from that of the blue pigment, wherein the dye has a structure represented by the following general formula (I) arranged on a metal atom or a metal compound position metal complex compound, and a dye is at least one selected from triphenylmethane dyes, (C) comprises a polymerizable compound, wherein the (B) more than 15 wt% of the dye the (a ) A colored photosensitive composition adsorbed on the surface of a blue pigment.
<2> The colored photosensitive composition according to <1>, including a dispersion composition obtained by dispersing the (A) blue pigment and the (B) dye in the same system.

<3> The dispersion composition is prepared by adjusting the concentration of the dye (B) in the dispersion composition in the initial stage of dispersion to Ci, and adjusting the concentration for preparing a colored photosensitive composition after the dispersion is completed. when the concentration of the (B) the dye in the object and Cf, Ci> Ru dispersion composition der satisfying the relation of Cf <colored photosensitive composition according to 2>.

<4> The (A) blue pigment is PB 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16 , 22 , 60 , 64 , 66 , 79 , 7 that 9 of the Cl was changed to OH, and at least one selected from 80 the group of <1> to colored photosensitive composition according to any one of <3>.

In general 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, halogen, An atom, an alkyl group, an aryl group, or a heterocyclic group is represented.

<5> Any one of <1> to <4>, including a dispersion composition obtained by premixing the (A) blue pigment and the (B) dye, and then dispersing the obtained color material composition The colored photosensitive composition of Claim 1.
<6> The colored photosensitive composition according to any one of <1> to <5>, further comprising (D) a photopolymerization initiator.

<7> The colored photosensitive composition according to any one of <1> to <6>, further comprising (E) an alkali-soluble binder.
<8> A color filter produced using the colored photosensitive composition according to any one of <1> to <7>.

<9> A colored layer forming step of forming a colored layer by applying the colored photosensitive composition according to any one of <1> to <7> on a support, and patterning the formed colored layer A method for producing a color filter comprising: an exposure step of exposing in a similar manner; and a development step of developing a colored layer after exposure to form a colored pattern.
<10> A display device comprising the color filter according to <8> or the color filter obtained by the production method according to <9>.

  In the present invention, a blue pigment and a dye (having a mother skeleton different from that of the pigment) are used as the colorant, and a part of the dye is adsorbed on the surface of the blue pigment, so that the surface of the blue pigment becomes a dye molecule. It is estimated that it is covered with. Since the dye is adsorbed to the pigment and is fixed to the pigment surface, the molecular movement of the dye is suppressed, and it is considered that the dye is suppressed from being decomposed even when heated, and the colored photosensitive composition of the present invention It is considered that the discoloration of the colored layer formed by using can be suppressed even by heating. On the other hand, since the blue pigment is coated with a dye, the coated dye acts as a protective colloid even when the blue pigment becomes fine due to dispersion or the like, and the dispersion state of the pigment is kept stable, thereby stabilizing the dispersion of the blue pigment. It is presumed that the characteristics will improve and the contrast and the like will increase.

By simply mixing a dye (dye powder or a dye solution dissolved in an organic solvent) into the pigment dispersion, the dye generally does not adsorb to the pigment, or the adsorption rate is small even if adsorbed. Colored contrast, dispersed dispersion composition and a blue pigment and the dye directly, or previously preparing a colorant composition comprising a blue pigment and a dye, using a dispersion composition by dispersing the coloring material composition The colored photosensitive composition of the present invention obtained by preparing the photosensitive composition has a high adsorption rate of the dye to the pigment surface, so that the obtained colored layer has high heat resistance and high contrast. Is presumed to have been obtained.

ADVANTAGE OF THE INVENTION According to this invention, when colored layers, such as a color filter, are formed, the colored photosensitive composition which can form a colored layer with favorable heat resistance, a high brightness | luminance, and a high contrast can be provided.
In addition, according to the present invention, a color filter using the colored photosensitive composition, capable of displaying an image with high brightness and high contrast, a manufacturing method thereof, and good image quality provided with the color filter Can be provided.

The colored photosensitive composition of the present invention is (A) a blue pigment and (B) a dye having a mother skeleton different from that of the blue pigment, and the dye has a structure represented by the following general formula (I). One or more dyes selected from metal complex compounds coordinated to metal atoms or metal compounds and triphenylmethane dyes (hereinafter referred to as “specific dyes” as appropriate), and (C) polymerizable compounds And 15% by mass or more of the specific dye is adsorbed on the surface of the (A) blue pigment.
The adsorption rate of the specific dye on the surface of the blue pigment in the colored photosensitive composition is 15% by mass or more of the specific dye, and preferably 20% by mass or more. The upper limit of the amount of adsorption is preferably as high as possible from the gist of the present invention, but it may be 90% by mass or less because adsorption of the dispersant may be inhibited if the pigment surface is coated with a dye too much. It is practical.

In the present specification, “to” represents a range from the lower limit value to the upper limit value. In addition, in the notation of groups in the present specification, the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent.
Further, in the present specification, the “total solid content of the colored photosensitive composition” refers to the total of the remaining components excluding the organic solvent from all the components constituting the colored photosensitive composition.
Furthermore, in the present invention, the adsorption rate of the dye to the pigment surface is determined by centrifuging the dispersion composition at 50000 rpm with an ultracentrifuge (manufactured by Hitachi Koki Co., Ltd.), collecting a supernatant containing free components, The amount of the dye in the obtained supernatant was measured by HPLC, defined as the dye adsorption rate obtained by the following formula, and expressed in%.

<Colored photosensitive composition>
Below, the essential component and arbitrary component which comprise the colored photosensitive composition of this invention are demonstrated.
The colored 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 contains (A) a blue pigment, and as the blue pigment, either a blue organic pigment or a blue inorganic pigment can be used, but a blue organic pigment is preferred.
Examples of the blue organic pigment include C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH And 80 are preferred, and among these, C.I. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, and 66 are preferred.

Further, considering that the average primary particle size of the blue pigment is preferably high transmittance, it is preferable to select a pigment having a particle size as small as possible and a fine particle size. Considering handling property in particular, the pigment preferably has an average primary particle diameter of 0.01 μm to 0.3 μm, more preferably 0.01 μm to 0.15 μm. When the particle size is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast.
The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

If necessary, the colored photosensitive composition of the present invention may be used in combination with an organic pigment other than a blue pigment or an inorganic pigment for color adjustment.
Examples of the pigments other than the blue pigment that can be used in combination include the following organic pigments. However, the present invention is not limited to these.
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73
C. I. Pigment Green 7, 10, 36, 37, 58
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28
C. I. Pigment Black 1

Among these, organic pigments that can be preferably used include the following.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32
C. I. Pigment Green 7, 36, 37, 58
C. I. Pigment Black 1

  In addition, examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, Examples thereof include metal oxides such as antimony and complex oxides of the above metals.

[(B) Specific dye]
The colored photosensitive composition of the present invention includes (A) a dye having a mother skeleton different from the blue pigment (= specific dye).
The mother skeleton is a structural part that characterizes the structure and hue of the dye, and includes, for example, structures such as phthalocyanine, pyromethene, and anthraquinone.
The specific dye is not particularly limited as long as it is a dye having a mother skeleton different from that of the blue pigment, and the chemical structure is pyromethene, pyrazoleazo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene. , Oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran and indigo dyes can be used.

  Specific examples thereof include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, US Patent. No. 4,808,501, U.S. Pat.No. 5,667,920, U.S. Pat.No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-11-302283 7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215 JP-A-11-343437, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, The dyes described in Kaihei 8-302224, JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

(Dipyrromethene metal complex compound)
Among these specific dyes, specific dyes suitable for the colored photosensitive composition of the present invention include metal complex compounds in which the structure represented by the following general formula (I) is coordinated to a metal atom or a metal compound (hereinafter, It is preferably referred to as “dipyrromethene-based gold complex compound” as appropriate.
The dipyrromethene metal complex compound in which the compound represented by formula (I) is coordinated to a metal atom or a metal compound will be described in detail.

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

  Examples of the monovalent substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, straight chain, branched chain, Or a cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl Group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, for example, vinyl Group, allyl group, 3-buten-1-yl group), aryl group (preferably having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms). An aryl group, for example, a phenyl group, a naphthyl group), a heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group, for example, a 2-thienyl group, a 4-pyridyl group 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably having 3 to 38 carbon atoms) More preferably a silyl group having 3 to 18 carbon atoms, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group An alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms such as a methoxy group, Butoxy group, 1-butoxy, 2-butoxy group, isopropoxy group, t-butoxy group, a dodecyloxy group, also, if a cycloalkyl group, for example, cyclopentyloxy group, cyclohexyloxy group),

An aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably an aryloxy group having 6 to 24 carbon atoms, such as a phenoxy group or 1-naphthoxy group), a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, More preferably, it is a heterocyclic oxy group having 1 to 18 carbon atoms, for example, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group), silyloxy group (preferably having 1 to 32 carbon atoms, more preferably A silyloxy group having 1 to 18 carbon atoms, for example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, a diphenylmethylsilyloxy group, an acyloxy group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms). Acyloxy groups such as acetoxy, pivaloyloxy, benzoyloxy, dodecano An alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, and a cycloalkyl group). If it is an oxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxy Carbonyloxy group), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-feni A carbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group),

An alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group), an arylsulfonyloxy A group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, more preferably 1 carbon atom). To 24 acyl groups, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably 2 carbon atoms). To 24 alkoxycarbonyl groups, for example A xoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), an aryloxycarbonyl group (preferably having 7 to 32 carbon atoms, More preferably, it is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group, and a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a carbamoyl group. N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N-dicyclohexyl A carbamoyl group), an amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, 2- Ethylhexylamino group, cyclohexylamino group),

Anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as an anilino group or N-methylanilino group), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably 1 A heterocyclic amino group having ˜18, for example, 4-pyridylamino group), a carbonamido group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, an acetamide group, a benzamide group, tetradecane Amide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferably ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido group, N, N-dimethylureido group, N- Phenylureido group) and imide group (preferably having 36 or less carbon atoms, more preferably having 24 or less carbon atoms) An N-succinimide group, an N-phthalimido group, an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as a methoxycarbonylamino group, ethoxy A carbonylamino group, a t-butoxycarbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamino group), an aryloxycarbonylamino group (preferably having 7 to 32 carbon atoms, more preferably having 7 to 24 carbon atoms) An amino group, for example, a phenoxycarbonylamino group), a sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methanesulfonamide group, a butanesulfonamide group, Benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenylazo Group, 3-pyrazolylazo group),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably having 6 to 48 carbon atoms). More preferably, it is an arylthio group having 6 to 24 carbon atoms, such as a phenylthio group, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, Dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 32 carbon atoms, more preferably An arylsulfinyl group having 6 to 24 prime atoms, such as a phenylsulfinyl group, an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as a methylsulfonyl group, ethyl Sulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably having 6 to 48 carbon atoms, more preferably An arylsulfonyl group having 6 to 24 carbon atoms, for example, a phenylsulfonyl group, 1-naphthylsulfonyl group), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, Rufamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl Groups (preferably phosphonyl groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphinoylamino groups (preferably A phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino group).

  When the above-described monovalent group is a further substitutable group, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.

In the general formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to each other to form 5, 6 or 7 members. The ring may be formed. In addition, as a ring formed, there exists a saturated ring or an unsaturated ring. Examples of the 5-membered, 6-membered, or 7-membered saturated ring or unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
In addition, when the formed 5-membered, 6-membered, and 7-membered rings are further substitutable groups, they may be substituted with any of the substituents R, and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.
In the general formula (I), when R ⁷ is a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, these preferred ranges are the halogen atom, alkyl group, and R ^{1 to} R ⁶ described above. This is the same as the preferred range of the aryl group or heterocyclic group.

In the general formula (I), the R ¹ and R ⁶ are preferably an alkylamino group, an arylamino group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, or a sulfonamide group among the above. An amide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are more preferable, and a carbonamide group and a ureido group are particularly preferable.

In the general formula (I), as R ² and R ⁵ , among the above, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group Preferred are alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoyl. A sulfonyl group is more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
In the general formula (I), R ³ and R ⁴ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and more preferably A substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group;

In general formula (I), when R ³ and R ⁴ represent an alkyl group, the alkyl group is preferably a linear, branched or cyclic substituted or unsubstituted alkyl having 1 to 12 carbon atoms. More specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, t-butyl group, cyclobutyl group, cyclopentyl group , A cyclohexyl group, and a benzyl group, more preferably a branched chain having 1 to 12 carbon atoms, or a cyclic substituted or unsubstituted alkyl group, and more specifically, for example, isopropyl group, cyclopropyl Group, i-butyl group, t-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and more preferably, a secondary or tertiary substitution having 1 to 12 carbon atoms or An unsubstituted alkyl group, more specifically, for example, an isopropyl group, a cyclopropyl group, an i-butyl group, a t-butyl group, a cyclobutyl group, and a cyclohexyl group.

In the general formula (I), when R ³ and R ⁴ represent an aryl group, the aryl group preferably includes a substituted or unsubstituted phenyl group and a substituted or unsubstituted naphthyl group, more preferably Is a substituted or unsubstituted phenyl group.
When 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, a substituted or unsubstituted 3 -Pyridyl group, substituted or unsubstituted 2-pyridyl group, substituted or unsubstituted 2-furyl group, substituted or unsubstituted 2-pyrimidinyl group, substituted or unsubstituted 2-benzothiazolyl group, substituted or unsubstituted 1 -Imidazolyl group, substituted or unsubstituted 1-pyrazolyl group, substituted or unsubstituted benzotriazol-1-yl group, more preferably substituted or unsubstituted 2-thienyl group, substituted or unsubstituted 4- Examples include a pyridyl group, a substituted or unsubstituted 2-furyl group, a substituted or unsubstituted 2-pyrimidinyl group, and a substituted or unsubstituted 1-pyridyl group.

Next, the metal atom or metal compound that forms the dipyrromethene-based metal complex compound will be described.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or 2 Valent metal chlorides are included. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ Further, metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is preferable. Most preferred. Among these, Zn is particularly preferable.

In the dipyrromethene metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound, preferred embodiments are shown below. That is, in general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy Group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone Represented by an amide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, wherein R ² and R ⁵ are each independently a hydrogen atom, a halogen atom, Atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxy Sil group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group , An alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, Aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamido group, ureido group, imide group An alkoxycarbonylamino group, Ruhon'amido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, represented by a sulfamoyl group, or a phosphinoylamino group, R ⁷ is a hydrogen atom, a halogen atom, an alkyl group , An aryl group, or a heterocyclic group, and the metal atom or metal compound is represented by Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO Is mentioned.

The more preferable aspect of a dipyrromethene type metal complex compound is shown below. That is, in the general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, Amino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group R ² and R ⁵ are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide Group, alkylsulfonyl group, arylsulfonyl group, or sulfa Represented by a moyl group, and R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, carbonamido group, It is represented by a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ⁷ is a hydrogen atom or a halogen atom. , An alkyl group, an aryl group, or a heterocyclic group, and a metal atom or metal compound is represented by Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO.

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

In the general formula (I-3), R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, Represents an aryl group or a heterocyclic group. R ⁸ and R ⁹ each independently represents 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 are each independently NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or Represents a sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, Represents a sulfur atom or a carbon atom. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed.

Formula ^{(I-3) R 2 ~R} 5 in, and ^{R 7,} the general formula (I) ^R 2 ~R ⁵ in, and have 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 has the same meaning as the metal atom or the metal compound in the complex in which the compound represented by the general formula (I) is coordinated to the metal atom or the metal compound. The preferred range is also the same.

In General Formula (I-3), R ⁸ and R ⁹ are each independently 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 group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl Group), an alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (preferably a carbon number). An aryl group having 6 to 36, more preferably 6 to 18, for example, a phenyl group or a naphthyl group, or a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 1 carbon atoms). 2 heterocyclic groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, Triazol-1-yl group), an alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms such as methoxy group, ethoxy group, propyloxy group, butoxy group, hexyloxy group, 2 -Ethylhexyloxy group, dodecyloxy group, cyclohexyloxy group), aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 1 to 18, for example, phenoxy group, naphthyloxy group), alkylamino A group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms such as Ruamino group, ethylamino group, propylamino group, butylamino group, hexylamino group, 2-ethylhexylamino group, isopropylamino group, t-butylamino group, t-octylamino group, cyclohexylamino group, N, N-diethylamino Group, N, N-dipropylamino group, N, N-dibutylamino group, N-methyl-N-ethylamino group), arylamino group (preferably C6-C36, more preferably 6-18 aryl) Amino group, for example, phenylamino group, naphthylamino group, N, N-diphenylamino group, N-ethyl-N-phenylamino group), or heterocyclic amino group (preferably having 1 to 24 carbon atoms, more preferably 1-12 heterocyclic amino groups such as 2-aminopyrrole group, 3-aminopyrazole group, 2-aminopyridine Down group, a 3-aminopyridine group).

In general formula (I-3), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group represented by R ⁸ and R ⁹ Is a further substitutable group, it may be substituted with any of the aforementioned substituents R, and when it is substituted with two or more substituents, these substituents are the same. It may or may not be.

In General Formula (I-3), X ³ and X ⁴ each independently represent NRa, an oxygen atom, or a sulfur atom. Ra is a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 24 carbon atoms, more Preferably it is a 2-12 alkenyl group, for example, a vinyl group, an allyl group, 3-buten-1-yl group), an aryl group (preferably a C6-C36, more preferably a 6-18 aryl group, For example, a phenyl group, a naphthyl group), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, Nyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), acyl group ( Preferably it is a C1-C24, more preferably C2-C18 acyl group, for example, an acetyl group, a pivaloyl group, a 2-ethylhexyl group, a benzoyl group, a cyclohexanoyl group), an alkylsulfonyl group (preferably a carbon number of 1 To 24, more preferably an alkylsulfonyl group having 1 to 18, for example, methylsulfonyl group, ethylsulfonyl group, isopropylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably having 6 to 24 carbon atoms, more preferably 6). To 18 arylsulfonyl groups such as phenylsulfonyl group, It represents a Chirusuruhoniru group). Further, when Ra can be substituted, it may be further substituted with a substituent, and when it is substituted with a plurality of substituents, these substituents may be the same or different.
X ³ and X ⁴ are preferably each independently an oxygen atom or a sulfur atom, and particularly preferably both X ³ and X ⁴ are oxygen atoms.

In 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 X ³ above.
Y ¹ and Y ² are preferably each independently NRb (Rb is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and Y ¹ and Y ² are particularly preferably both NH.

In general formula (I-3), R ⁸ and Y ¹ are bonded to each other, and together with R ⁸ , Y ¹ , and carbon atom, a 5-membered ring (eg, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole) , Furan, thiophene, indole, benzofuran, benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline) Or a 7-membered ring (eg, cycloheptane, hexamethyleneimine).

In General Formula (I-3), R ⁹ and Y ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with R ⁹ , Y ² , and the carbon atom. 5-membered to be formed, 6-membered, and 7-membered ring, the ring one bond in the ring formed by said R ⁸ and Y ¹ and the carbon atom is changed to the double bond.

In the general formula (I-3), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ⁸ and Y ¹ and R ⁹ and Y ² are further substitutable rings May be substituted with the group described in any of the substituents R, and when it is substituted with two or more substituents, these substituents may be the same or different. Good.

In General Formula (I-3), X ⁵ represents a group capable of binding to Ma, and examples thereof include the same groups as X ² in General Formula (I-1). a represents 0, 1, or 2.

Preferred embodiments of the compound represented by formula (I-3) are shown below. That is, R ^{2 to} R ⁵ , R ⁷ and Ma are each a preferred embodiment of a complex containing a compound represented by the general formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are Each independently NRa (Ra is a hydrogen atom, an alkyl group, a heterocyclic group) or an oxygen atom, 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 through an oxygen atom or a nitrogen atom, and R ⁸ and R ⁹ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group. R ⁸ and Y ¹ are bonded to each other to form a 5- or 6-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5- or 6-membered ring, a is 0 Or it is an aspect represented by 1.

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

  The general formulas (I-1), (I-2) and (I-) are preferred embodiments of the dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound. Among the complex compounds represented by 3), the complex compound represented by the general formula (I-3) is a particularly preferred embodiment.

  Hereinafter, specific examples of the dipyrromethene metal complex compound in which the compound represented by the general formula (I) used in the present invention is coordinated to a metal atom or a metal compound are shown. However, the present invention is not limited to these.

  Among the exemplary compounds of the dipyrromethene metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound, the exemplary compounds (1) to (39) are represented by the general formula (I-3). It is also an exemplary compound.

  In addition to the above exemplary compounds, exemplary compounds (Ia-3) to (Ia-83), (Ia-1) to (IIa-20), and (I-1) to (I) described in JP-A-2008-292970 -36) (II-1) to (II-11) and (III-1) to (III-103), Exemplified compounds (I-1) to (I-35) described in Japanese Patent No. 3324279, Patent No. Exemplified compounds (I-1) to (I-13) described in No. 3279035, Exemplified compounds (2-1) to (2-32) and (3-1) to (3-32) described in JP-A No. 11-256057 , (4-1) to (4-26), and (5-1) to (5-26), exemplified compounds (I-1) to (I-6) and (VII) described in JP-A-2005-77953 -1) to (VII-8), exemplified compounds (1-1) to (1-45) described in JP-A No. 11-352686, JP-A 2000-197 Compound (1-1) to (1-50) described in 9 and compounds (1-1) to (1-45) described in JP-A No. 11-352585 are also represented by the general formula (I) Is an example of a dipyrromethene metal complex compound coordinated to a metal atom or a metal compound.

(Dispersion composition)
The colored photosensitive composition of the present invention preferably contains a dispersion composition. As a method for obtaining the colored photosensitive composition of the present invention, a dispersion composition preferably contained will be described.
In the colored photosensitive composition of the present invention, 15% by mass or more of the (B) specific dye is adsorbed on the surface of the (A) blue pigment. (B) By setting the adsorption rate of the specific dye to the surface of the blue pigment (A) in the above range, the colored layer obtained by the colored photosensitive composition of the present invention has good heat resistance and high contrast. Can show. The method for adsorbing the specific dye to the blue pigment may be any method, but it is preferable to prepare a dispersion composition containing the blue pigment and the specific dye in advance.

(Coloring material composition)
In order to obtain this dispersion composition, it is preferable that a blue pigment and a specific dye are preliminarily mixed to obtain a color material composition, and then a dispersion treatment is performed in the same system to obtain a dispersion composition. That is, a slurry (coloring material composition) in which pigments and dyes are mixed with a solvent, a dispersant, an additive, an abrasive, etc., as necessary, is prepared, and this is collectively put into a dispersion system for dispersion treatment. It is preferable. Therefore, in the present invention, before performing salt milling, which will be described later, or before performing dispersion processing with a disperser, and before performing each stage when performing multistage dispersion processing with a disperser. In the case where a slurry in which a dye is mixed in advance is dispersed, this is called premixing. The above “in the same system” means that the dispersion processing is performed in the same dispersion apparatus and in the same dispersion batch.
Various methods can be selected as the premixing method. The blue pigment and the solid specific dye may be mixed using the organic solvent (F) described later, or the blue pigment and the organic solvent (F) described below. A dye solution in which a specific dye is dissolved may be mixed.
The mixing method may be a method using a normal stirrer, etc., using a two-roll, three-roll, ball mill, tron mill, disper, kneader, conider, homogenizer, blender, single-screw or twin-screw extruder, etc. A method of kneading while applying a strong shearing force may be used, but a method of kneading is preferable from the viewpoint of increasing the adsorption rate of the dye.

(Salt milling)
Since the pigment is usually agglomerated and is crushed before being dispersed, it is preferable that a salt milling process described later is performed as the pigment refinement process. At this time, as a method of mixing the dye and the pigment, the color material composition can be prepared by adding a specific dye in a solution or solid state during the salt milling treatment.

Pigment refinement involves preparing a liquid composition with high viscosity together with pigment, water-soluble organic solvent, and water-soluble inorganic salts, and applying a stress using a wet crusher etc. to grind (salt milling) ) To achieve. At this time, if necessary, a specific dye may be added together with the pigment in the form of a solution or a solid to obtain a color material composition .

Water-soluble organic solvents used in the pigment refinement process include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Examples thereof include monobutyl ether, propylene glycol, propylene glycolic monomethyl ether acetate and the like.
In addition, other solvents having low or no water solubility, such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate , Hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. May be.
Only one type of solvent may be used in the pigment refinement step, or two or more types may be mixed and used as necessary.

Examples of the water-soluble inorganic salt used in the pigment refining step include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.
The amount of the water-soluble inorganic salt used in the miniaturization step is 1 to 50 times by mass of the pigment, and a larger amount has a grinding effect, but a more preferable amount is 1 to 10 times by mass in terms of productivity. Moreover, it is preferable to use inorganic salts having a moisture content of 1% or less.
The usage-amount of the water-soluble organic solvent in a refinement | miniaturization process is the range of 50 mass parts to 300 mass parts with respect to 100 mass parts of pigments, Preferably it is the range of 100 mass parts to 200 mass parts.

  There are no particular restrictions on the operating conditions of the wet pulverizer in the pigment refinement process. However, in order to effectively carry out the grinding with the pulverizing media, the operating condition when the apparatus is a kneader is the rotational speed of the blade in the apparatus. Is preferably 10 to 200 rpm, and a relatively large biaxial rotation ratio is preferable because of a large grinding effect. The operation time is preferably 1 to 8 hours in combination with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, the water-soluble inorganic salt that is a pulverization medium preferably has a pulverization particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

The composition ratio of the blue pigment and the specific dye in the color material composition is preferably 1: 1 to 10: 1, more preferably 2: 1 to 10: 1 in terms of mass. By setting it as this range, the adsorption rate of the specific dye on the surface of the blue pigment can be made 15 mass% or more of the specific dye, and the effects of the present invention can be exhibited.
Further, the total of the pigment and the dye in the color material composition is preferably 10% by mass to 60% by mass with respect to the total solid content in the color material composition.

(Method for producing dispersion composition)
The dispersion composition is obtained by dispersing a blue pigment and a specific dye using an organic solvent (F) described later. At this time, it is preferable to use the color material composition instead of the blue pigment and the specific dye.
Furthermore, the dispersant, pigment derivative, and other components described later may be added to the dispersion composition, and pigments other than the blue pigment may be added.

  In the dispersion composition of the present invention, the above-described components are added all at once or divided, and the particle size is 0.01 mm to 1 mm using a dispersing machine such as a vertical or horizontal sand grinder, a pin mill, or a slit mill. It can be obtained by performing fine dispersion treatment with beads made of glass, zirconia or the like.

In the case where the blue pigment and the specific dye are dispersed without passing through the colorant composition without being premixed in advance, it is preferable to introduce the dye into the dispersing apparatus during the dispersion of the pigment, and particularly at the initial stage of the dispersion. It is preferable to add in stages. In this case, since it is not preferable to add a large amount of dye at a time, it is not preferable.
In addition, when adding the specific dye into the dispersing apparatus, a dye solution of the specific dye may be added, but it is preferable to add in a solid state if possible in view of solubility. Even when the dye solution is added, it is preferable that the dye concentration after the addition is as high as possible. This is because the higher the concentration of the dye in the system of the dispersion composition, the more the adsorption to the pigment is promoted, and as a result, the heat resistance improvement which is the effect of the present invention is easily achieved. From this point of view, the dye is preferably added at the time of salt milling or at the beginning of dispersion. When multistage dispersion described later is used, it is preferably carried out at the beginning of the first stage of dispersion.
As a method for preparing the dye solution, an organic solvent may be added to the dye and stirred, but a method of adding a powdered dye into the stirred organic solvent is preferable in terms of easy dissolution. As for the method of adding the dye, the entire amount may be added at once, but it is also possible to add it in divided portions.

  As a method for dissolving the dye, the above-mentioned solution containing the dye and the organic solvent may be stirred with a rod-like one, or a magnetic stirrer may be used, and a propeller-like stirrer is fixed in the container. What is necessary is just to melt | dissolve with the normal stirrer rotated to speed and one direction. Further, it may be dissolved by applying a shearing force with a mixer, a dissolver or the like. If necessary, it may be dissolved by heating.

In addition, before carrying out fine dispersion with beads, use a two-roll, three-roll, ball mill, tron mill, disper, kneader, conifer, homogenizer, blender, single or twin screw extruder, etc. It is also possible to perform the kneading process while feeding.
The details of kneading and dispersing are described in “Paint Flow and Pigment Dispersion” by TCPatton (1964, published by John Wiley and Sons), etc., and the method described here should also be applied in the present invention. Can do.

Further, in the dispersion, at the initial stage of dispersion, the solid content in the dispersion composition is set higher than the solid content of the final dispersion composition, and when the dispersion approaches the end of the dispersion, organic solvents and other A method of diluting with components other than coloring components such as a polymer compound is also a preferred embodiment.
In a preferred embodiment of the method for preparing the dispersion composition, the dispersion is typically carried out in two stages of coarse dispersion and fine dispersion, or further divided into multiple stages.
That is, 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 completion of dispersion (in the case of adjusting the concentration after completion of dispersion, the concentration of the specific dye after concentration adjustment) In order to satisfy the relationship of Ci> Cf when Cf is set, it is preferable to perform dispersion by taking two or more steps.
When premixing is performed, Ci is the concentration of the specific dye in the premixing. When premixing is not performed, the first-stage dispersion (in the two-stage dispersion) It is the concentration of the specific dye in the (coarse dispersion), and when it is dispersed in one stage without premixing, it is the concentration of the specific dye at the start of dispersion. Cf is the concentration of the specific dye at the final stage of dispersion (precision dispersion in the case of two-stage dispersion). When the concentration is adjusted after dispersion, the concentration of the specific dye after concentration adjustment corresponds to the above-mentioned Cf.

By doing so, not only does the dye more easily adsorb on the pigment surface under high concentration, but also the dye gradually adsorbs on the pigment surface as the pigment disperses and progresses while achieving adsorption equilibrium. It is possible to increase the adsorption rate. When Ci = Cf, even if the above density adjustment is finally performed, it takes time to reach the adsorption equilibrium because the dye concentration is already low from the time of introduction. This is not preferable because the typical adsorption rate may be low.
Further, according to this method, since the solid content is large at the initial stage of dispersion, a high shearing force is applied to the dispersion, and the dispersion of the pigment is facilitated by this shearing, and high dispersibility is obtained.
Further, Ci is preferably set to 1.1 to 10 times Cf, and more preferably 1.1 to 5 times. By setting it within this range, a dispersion composition having high dispersibility can be easily obtained.

(Other components contained in the dispersion composition)
Hereinafter, the dispersant and the pigment derivative that are preferably contained in the dispersion composition of the present invention will be described.

(Dispersant)
Specifically, many types of compounds can be used as the dispersant. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants (manufactured by Nippon Lubrizol Corp.) such as 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and Ionnet S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 62,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (manufactured by BYK-CHEMIE Co., Ltd.).

-Polymer dispersant-
The dispersion composition in the present invention preferably contains a polymer dispersant described below as a dispersant.
The dispersion composition in the present invention is a polymer compound having at least one structural unit represented by the following general formula (II) or the following general formula (III) and at least one structural unit having an acid group (Hereinafter sometimes referred to as “specific polymer”).

In the general formulas (II) and (III), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent —CO—, —C (═O ) O—, —CONH—, —OC (═O) — or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and A ¹ and A ² each independently Represents a monovalent organic group, m and n each independently represents an integer of 2 to 8, and p and q each independently represents an integer of 1 to 100.

(Structural unit represented by general formula (II) or general formula (III))
The structural unit represented by the general formula (II) or the general formula (III) is included as a repeating unit in the polymer compound (A).

In the general formula (II) and general formula (III), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As an alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.
When the alkyl group has a substituent, examples of the substituent include a hydroxy group, an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Examples include a cyclohexyloxy group.
Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, A 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group are exemplified.
R ¹ , R ² , R ⁴ , and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are most preferably hydrogen atoms or methyl groups from the viewpoint of adsorption efficiency on the pigment surface.

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

L ¹ and L ² each independently represents 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 comprising 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, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. In addition, examples of the hetero atom in the partial structure containing a hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom, and among them, an oxygen atom and a nitrogen atom are preferable.
Specific examples of preferable alkylene groups include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the alkylene group has a substituent, examples of the substituent include a hydroxy group.
The divalent organic linking group includes a heteroatom or a heteroatom selected from —C (═O) —, —OC (═O) —, and —NHC (═O) — at the end of the alkylene group. A compound having a partial structure and linked to an adjacent oxygen atom via the heteroatom or a partial structure containing a heteroatom is preferable from the viewpoint of adsorptivity to the pigment.

A ¹ and A ² each independently represents a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable.
Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N '-Arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-aryluree Id group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group An alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), Alkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate) Group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (— OPO _{3 (aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )) Monoalkyl phosphono group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugate Examples thereof include a base group (hereinafter referred to as an arylphosphonatoxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, and a silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.
Examples of the substituent include an alkoxy group, aryloxy group, alkylthio group, arylthio group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, aryl group, hetero An aryl group, an alkenyl group, an alkynyl group, and a silyl group are preferable from the viewpoint of dispersion stability.

  Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group It can be exemplified phosphonophenyl phenyl group.

As A ¹ and A ² , from the viewpoint of dispersion stability and developability, a straight chain having 1 to 20 carbon atoms, a branched structure having 3 to 20 carbon atoms, and a number having 5 to 20 carbon atoms can be used. Cyclic alkyl groups are preferable, linear alkyl groups having 4 to 15 carbon atoms, branched alkyl groups having 4 to 15 carbon atoms, and cyclic alkyl groups having 6 to 10 carbon atoms are more preferable. Even more preferred are linear alkyl groups of 6 to 10 and branched alkyl groups of 6 to 12 carbon atoms.

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

  p and q each independently represents an integer of 1 to 100. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.

The specific polymer in the present invention contains at least one structural unit represented by the general formula (II) or at least one structural unit represented by the general formula (III), or contains the general formula (II). And at least one structural unit represented by the general formula (III). Here, in the general formulas (II) and (III), the following combinations are particularly preferable embodiments. That is, R ¹ , R ² , R ⁴ , and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are preferably hydrogen atoms or methyl groups. X ¹ and X ² are preferably —C (═O) O—. L ¹ and L ² are each a hetero atom or hetero atom selected from —C (═O) —, —OC (═O) —, and —NHC (═O) — at the terminal of an alkylene group having 1 to 4 carbon atoms. And a divalent organic linking group linked to an adjacent oxygen atom through the heteroatom or a partial structure containing a heteroatom. m and n are preferably 5, and p and q are preferably 5 to 20.

As the specific polymer in the present invention, a polymer containing at least one structural unit represented by the general formula (II) is preferable from the viewpoint of dispersion stability.
The structural unit represented by the general formula (II) is more preferably a structural unit represented by the following general formula (II) -2.

In the general formula (II) -2, R ^{1 to} R ³ each independently represents 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 to 8, and p represents an integer of 1 to 100.
The monovalent organic group represented by R ^{1 to} R ³ and A ¹ , and details and preferred embodiments of m and p are the same as those in the general formula (II).
La is more preferably an alkylene group having 2 to 8 carbon atoms, and further preferably an alkylene group having 2 to 4 carbon atoms. Specific examples include an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group. When the alkylene group has a substituent, examples of the substituent include a hydroxy group.

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

In the general formulas (i), (ii) and (i) -2, R ^{1 to} R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent —CO—. , -C (= O) O-, -CONH-, -OC (= O)-or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group, and La represents Represents an alkylene group having 2 to 10 carbon atoms, Lb represents —C (═O) — or —NHC (═O) —, A ¹ and A ² each independently represents a monovalent organic group, m and n each independently represents an integer of 2 to 8, and p and q each independently represents an integer of 1 to 100.
R ^{1 to} R ⁶ , X ¹ and X ² , L ¹ and L ² , A ¹ and A ² , m and n, p and q are the same as those in the general formulas (II), (III) and (II) -2. It is synonymous.

  Hereinafter, preferred specific examples of the monomer represented by the general formula (i), (ii) or (i) -2 [monomers (A-1) to (A-24)] will be given. Is not limited to these.

  The specific polymer in the present invention includes at least one of the structural units represented by the general formula (II) or (III), and may include only one or may include two or more. .

  Further, in the specific polymer, the content of the structural unit represented by the general formula (II) or (III) is not particularly limited, but the total structural unit contained in the polymer is 100% by mass. In addition, the structural unit is preferably contained in an amount of 5% by mass or more, more preferably 30% by mass or more, and 40% by mass to 60% by mass in view of achieving both dispersibility and developability of the pigment. Is more preferable.

(Structural unit having an acid group)
The specific polymer in this invention contains the structural unit (acid group containing structural unit) which has an acid group. The acid group of the acid group-containing structural unit serves as an adsorbing group for the pigment or pigment derivative.

  In the acid group-containing structural unit in 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 these, a carboxylic acid group is most preferably used from the viewpoint of achieving 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 a linking chain.
The linking chain linking the main chain and the acid group of the specific polymer is a linking group containing a functional group selected from an aromatic ring, an ether group, an ester group, an amide group, a urea group and / or a urethane group. Is preferred. Since the functional group itself exhibits an adsorptive property to the pigment, it is considered that when the functional group is located close to the acid group in the acid group-containing structural unit, the adsorptivity to the pigment or the pigment derivative is increased. .
Here, the main chain of the specific polymer means a site linked by polymerization when the polymer is synthesized. For example, in the case of a polymer obtained by polymerizing a methacrylic acid ester, it means an alkylene site where the methacrylic sites are linked by polymerization. .

Moreover, the said coupling group can be used combining multiple types of coupling 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, an ether group, and a urea group can be used in combination.

  When the dispersion composition of the present invention contains titanium black as a pigment, since the titanium black has a nitrogen atom, a hydrogen bonding functional group is preferably used as the linking group of the specific polymer. A group and a urethane group are preferably used.

Moreover, it is preferable to introduce | transduce an aromatic ring as a coupling group used for the acid group containing structural unit in this invention. By having an aromatic ring in the linking chain, the entanglement of the polymer can be reduced due to steric hindrance compared to a normal alkyl chain, etc., and the aromatic ring can easily be directed out of the polymer from the main chain part. Can be improved.
Here, the aromatic ring represents a structure in which atoms having π electrons are arranged in a ring, and includes a ring not containing a hetero atom such as a benzene ring, a naphthalene ring, and an anthracene ring, a pyridine ring, a pyrrole ring, a furan ring, and a carbazole. Various rings such as a ring and a ring containing a hetero atom such as a thiophene ring can be used. Among them, a highly versatile benzene ring, naphthalene ring, and pyridine ring can be preferably used, and a benzene ring can be more preferably used, and has a structure represented by the following formula (2). More preferred.

  In said formula (2), Y represents a coupling group with the principal chain of a specific polymer, and S represents an acidic functional group. R is 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, and may have a substituent. An aryloxy group, a heteroaryloxy group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent. Represents an optionally substituted alkylamide group, an optionally substituted arylamide group, a halogen group, and a nitro group. N represents an integer of 0 to 4, and m represents an integer of 1 to 5.

In said formula (2), Y represents a coupling group with the principal chain of a specific polymer. The structure of the linking group is not particularly limited, but from the viewpoint of lowering the pKa of the acid group, it is preferable that the benzene ring and the main chain are linked by an electron withdrawing group, and an ester group, an amide group, a sulfonamide group It is more preferable that they are connected with each other, and it is more preferable that they are connected with an ester group.
Although the preferable specific example of Y is shown below, Y is not necessarily limited to these structures. X represents the site | part couple | bonded with the principal chain of a specific polymer, and Z represents the site | part couple | bonded with a benzene ring.

  In the formula (2), R is 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, or a substituent. An aryloxy group which may have a substituent, a heteroaryloxy group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, an aryloxy which may have a substituent A carbonyl group, an optionally substituted alkylamide group, an optionally substituted arylamide group, a halogen group, and a nitro group are represented. From the viewpoint of lowering the pKa of the acid group, it is preferably substituted with a hydrogen atom or an electron withdrawing group, and has a hydrogen atom, an alkyloxycarbonyl group which may have a substituent, or a substituent. Preferably an aryloxycarbonyl group, an optionally substituted alkylamide group, an optionally substituted arylamide group, a halogen group, a nitro group, or a carboxyl group, a hydrogen atom, More preferred are an alkyloxycarbonyl group which may have an aryloxycarbonyl group which may have a substituent.

  The acid group-containing structural unit in the present invention is preferably a structural unit having a carboxylic acid group as an acid group (hereinafter sometimes referred to as “carboxylic acid group-containing structural unit”). More preferably, it is a structural unit having a carboxylic acid group bonded to the main chain of the specific polymer through a linking chain composed of an atomic group having 4 or more atoms excluding hydrogen atoms.

In the carboxylic acid group-containing structural unit, since the carboxylic acid group is bonded to the main chain via a linking chain, the flexibility of the carboxylic acid group portion is increased, and the pigment or pigment derivative is more efficiently interacted with the pigment or pigment derivative. It becomes possible to act. In addition, since the carboxylic acid group also functions as a developable group, the developability is improved by increasing the flexibility. In this respect, a longer connecting chain is preferable.
On the other hand, if the linking chain is too long, the number of carboxylic acid group-containing structural units that can be introduced into the polymer decreases, so that the number of carboxylic acid groups that can be introduced into the polymer decreases.
From the above, in the carboxylic acid group-containing structural unit, the connecting chain connecting the main chain and the carboxylic acid group is composed of an atomic group having 4 to 100 atoms excluding hydrogen atoms. More preferably, it is composed of an atomic group having 6 to 60 atoms excluding hydrogen atoms, and more preferably 8 to 20 atoms excluding hydrogen atoms. It consists of individual atomic groups.

  In the carboxylic acid group-containing structural unit, the preferred embodiment of the linking chain that connects the main chain of the specific polymer and the carboxylic acid group is the same as the linking chain in the acid group-containing structural unit described above, and the linking chain Similarly, a plurality of types of linking groups can be used in combination.

As the linking group used in the carboxylic acid group-containing structural unit, it is preferable to introduce an aromatic ring as in the case of the acid group-containing structural unit described above, and the preferred embodiment of the aromatic ring is the same.
The partial structure of the carboxylic acid group-containing structural unit is more preferably a structure represented by the following formula (1).

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

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

  In the carboxylic acid group-containing structural unit, the connecting chain preferably includes an atomic group having an aromatic ring and having 6 to 60 atoms excluding hydrogen atoms. More preferably, the aromatic ring is a benzene ring, and is a linking chain bonded to the main chain via the benzene ring or by an ester bond.

  In the specific polymer of the present invention, the content of the carboxylic acid group-containing structural unit is preferably 50 mgKOH / g or more from the viewpoint of suppressing the formation of precipitates in the developer when forming the colored region. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of secondary aggregates, the content of carboxylic acid group-containing structural units is: 50 mg KOH / g to 200 mg KOH / g.

(Other structural units)
The specific polymer in the present invention is preferably a polymer compound obtained by further copolymerizing a monomer having a functional group capable of adsorbing to the pigment for the purpose of enhancing the adsorptivity to the pigment.
Specific examples of monomers having functional groups that can be adsorbed to pigments other than acid groups include monomers having organic dye structures or heterocyclic structures, monomers having basic nitrogen atoms, and monomers having ionic groups. And so on. Among these, monomers having an organic dye structure or a heterocyclic structure are preferable from the viewpoint of the adsorptive power to the pigment.

  The monomer having a functional group capable of adsorbing to the pigment (monomer) can be appropriately selected according to the type of pigment to be dispersed, and these may be used alone or in combination of two or more. Good.

  The specific polymer in the present invention may further contain a structural unit derived from a copolymerizable vinyl monomer as long as the effect is not impaired.

  Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In the present specification, “(meth) acryl” may be described when either or both of “acryl and methacryl” are indicated.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  Specific examples of the specific polymer in the present invention include the following Exemplified Compound 1 to Exemplified Compound 35.

The preferred molecular weight of the specific polymer in the present invention is in the range of 5000 to 100,000 in terms of weight average molecular weight (Mw) and in the range of 2500 to 50000 in terms of number average molecular weight (Mn). More preferably, the weight average molecular weight (Mw) is in the range of 10,000 to 50,000, and the number average molecular weight (Mn) is in the range of 5,000 to 30,000. In particular, it is most preferable that the weight average molecular weight (Mw) is in the range of 20000 to 40000 and the number average molecular weight (Mn) is in the range of 5000 to 20000.
That is, the weight average molecular weight (Mw) of the specific polymer is 1000 or more from the viewpoint of effectively loosening the secondary aggregate, which is an aggregate of primary particles of the pigment, or effectively reducing reaggregation. It is preferable. Moreover, from the viewpoint of developability when producing a color filter from a colored photosensitive composition containing a dispersion composition, the weight average molecular weight (Mw) of the specific polymer is preferably 50,000 or less.

The specific polymer in the present invention can be produced by a normal radical polymerization method.
In general, a suspension polymerization method or a solution polymerization method is used. Examples of the solvent used for synthesizing such a specific polymer include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy. Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more. In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.

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

The dispersion composition can contain a pigment derivative.
A pigment derivative is a compound in which an acidic group, a basic group, or an aromatic group is introduced as a substituent in the 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 its surface, but a pigment derivative having a portion having an affinity for the specific polymer (polymer dispersing agent) is a pigment that does not adsorb the specific dye. By adsorbing on the surface and using this as the adsorption point of the specific polymer, the pigment can be dispersed in the colored composition as finer particles. Moreover, the reaggregation can also be prevented. That is, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant such as the specific polymer in the present invention by modifying the pigment surface on which the specific dye is not adsorbed.

  Since the specific polymer in 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 a fine pigment can be effectively used. Can be dispersed. Then, by using a colored photosensitive composition containing a basic pigment derivative, it is possible to form a color filter with further reduced color density unevenness and excellent color characteristics.

  The pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced as a substituent in the side chain. Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoic pigments. Examples include imidazolone pigments. In addition, the host skeleton also includes light yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds that are not generally called pigments.

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

  When using a pigment derivative in the dispersion composition in the present invention, the amount used is preferably in the range of 1% by mass to 80% by mass with respect to the pigment, and in the range of 3% by mass to 65% by mass. It is more preferable that it is in the range of 5% by mass to 50% by mass. When the content is within this range, the pigment can be favorably dispersed while keeping the viscosity low, and the dispersion stability after dispersion can be improved. By applying this 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.

Furthermore, as long as the effects of the present invention are not impaired, other polymer compounds may be used at the same time as the specific polymer in the present invention, if necessary. As other polymer compounds, natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like are used.
The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.
Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.

As content of the blue pigment in a dispersion composition, 20-70 mass% is preferable with respect to the total solid (mass) of a dispersion composition, and 30-60 mass% is more preferable. When the content of the blue pigment is within the above range, the color density is sufficient to ensure excellent color characteristics.
Moreover, as content of the specific dye in a dispersion composition, 5-40 mass% is preferable with respect to the total solid (mass) of a dispersion composition, and 10-30 mass% is more preferable. When the content of the specific dye is within the above range, the dispersion composition has good dispersion stability, and is effective in securing excellent color characteristics with sufficient color density.

Moreover, it is preferable that content of the blue pigment in the colored photosensitive composition of this invention is 1-50 mass% with respect to the total solid of this composition, and 1-30 mass% is more preferable.
Furthermore, it is preferable that content of the specific dye in the coloring photosensitive composition of this invention is 0.1-25 mass% with respect to the total solid of this composition, 0.1-15 mass% Is more preferable. When the content of the pigment and the specific dye is within the above range, the colored layer obtained using the colored photosensitive composition has high luminance and high contrast, and the colored photosensitive composition such as developability. It is easy to satisfy various characteristics required for the above.

[(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 and used from components constituting a known composition, as disclosed in JP-A-2006-23696. Examples include the components described in paragraph numbers [0010] to [0020] and the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921.

In addition, a urethane-added polymerizable compound produced by using an addition reaction between an isocyanate and a hydroxyl group is also suitable. JP-A-51-37193, JP-B-2-32293, JP-B-2-16765 And the ethylene oxide skeletons described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Urethane compounds having them are also suitable.
Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with acrylic acid. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate. , Pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc., and commercially available products include NK ester A-TMMT, NK ester A-TMM-3, NK oligo UA -32P, NK Oligo UA-7200 (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronic M-402, TO-1382, TO-2349 (manufactured by Toagosei Co.), V # 802 (manufactured by Osaka Organic Chemical Industry Ltd.) can be cited as a preferred example.

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

These polymerizable compounds can be used alone or in combination of two or more.
The content of the polymerizable compound in the total solid content in the colored photosensitive composition (the total content in the case of two or more) is preferably 10% by mass to 80% by mass, and 15% by mass to 75% by mass. More preferably, 20% by mass to 60% by mass is particularly preferable.

[(D) Photopolymerization initiator]
The colored photosensitive composition of the present invention preferably contains at least one photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
The photopolymerization initiator is a compound that is exposed to exposure light and starts and accelerates polymerization of the polymerizable compound. A compound that responds to actinic rays having a wavelength of 300 nm or longer and initiates and accelerates polymerization of the polymerizable compound is preferable. In addition, a photopolymerization initiator that does not directly respond to actinic rays having a wavelength of 300 nm or longer can also be preferably used in combination with a sensitizer.

Specifically, for example, oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexa Examples thereof include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxides), benzophenone compounds, acetophenone compounds, and derivatives thereof.
Among these, oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity.

  Examples of the oxime ester compound include JP 2000-80068, JP 2001-233842, JP 2004-534797, WO 2005/080337, WO 2006/018933, JP The compounds described in JP 2007-210991 A, JP 2007-231000 A, JP 2007-2699779 A, JP 2009-191061 A, and International Publication No. 2009/131189 can be used.

  Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) Such as 9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  In the present invention, a compound represented by the following general formula (A) is also suitable as an oxime ester compound that is a photopolymerization initiator from the viewpoint of coloring in sensitivity, temporal stability, and heat resistance.

In the general 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 is —R, —OR, —COR, —SR, —CONRR. 'Or -CN, R ² and R ³ are each independently. -R, -OR, -COR, -SR, or -NRR 'is represented. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. And one or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. May form a ring.

In general formula (A), when X ¹ , X ² , and X ³ represent a halogen atom, examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and X ¹ , X ² , and X ³ are alkyl. Examples of the alkyl group in the case of representing a group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2- Ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxypropyl, Monofluoromethyl, difluoromethyl, Fluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2'-yl) ethenyl and the like.
Especially, it is preferable that all of X < ¹ >, X < ² > and X < ³ > represent a hydrogen atom, or X < ¹ > represents an alkyl group and X < ² > and X < ³ > both represent a hydrogen atom.

In general formula (A), examples of the alkyl group represented by R and R ′ include methyl,
Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, Vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl , Perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like.
Examples of the aryl group represented by R and R ′ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like.
Examples of the aralkyl group represented by R and R ′ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like.
Examples of the heterocyclic group represented by R and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl and the like.
Examples of the ring formed by bonding R and R ′ to each other include a piperidine ring and a morpholine ring.

R ² and R ^{3 including} R and R ′ are each independently a methyl group, a hexyl group, a cyclohexyl group, —S—Ph, —S—Ph—Cl, and —S—Ph—. Br is a particularly preferred embodiment.

Among the photopolymerization initiators, in general formula (A), X ¹ , X ² , and X ³ are all hydrogen atoms; R ¹ is an alkyl group, particularly a methyl group; R ² is alkyl Particularly preferred as photoinitiators are those which are groups, in particular methyl groups; those in which R ³ is an alkyl group, in particular ethyl group.

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

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

  The compound represented by the general formula (A) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

  In the present invention, a compound represented by the following general formula (B) is also suitable as an oxime ester compound that is a photopolymerization initiator from the viewpoint of sensitivity, stability over time, and coloring during post-heating.

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

The monovalent substituent represented by R ²² is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R ²² include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkylsulfonyl group that may have a substituent, Examples include an arylsulfonyl group which may have a substituent, an acyl 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, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, or a trifluoromethyl group. , Etc.

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

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

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

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The heterocyclic group that 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 pyranyl group, etc. are mentioned.

R ²² is more preferably an unsubstituted or substituted acyl group from the viewpoint of high sensitivity, and specifically, an unsubstituted or substituted acetyl group, propionyl group, benzoyl group, toluyl group. Groups are preferred.
Examples of the substituent include groups represented by the following structural formula, and among these, any of (d-1), (d-4), and (d-5) is preferable.

Examples of the divalent linking group represented by A ^22, alkylene having 1 to 12 carbon atoms which may have a substituent, may cyclohexylene which may have a substituent and may have a substituent Alkynylene is mentioned.
Examples of the substituent that can be introduced into these groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Examples include aryloxy groups such as a tolyloxy group, alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group.

Among these, A ²² is substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Alkylene group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, An alkylene group substituted with a styryl group) is preferred.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent.
Specifically, Ar is phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m. -, P-cumenyl group, mesityl group, etc. are mentioned. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen atoms such as a fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy such as methoxy group, ethoxy group and tert-butoxy group. Groups, phenoxy groups, aryloxy groups such as p-tolyloxy groups, methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acetoxy groups, propionyloxy groups, acyloxy groups such as benzoyloxy groups, acetyl groups, Benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methacrylyl group and other acyl groups, methylamino group, cyclohexylamino group and other alkylamino groups, dimethylamino group, diethylamino group, morpholino group, piperidino group and other dialkylamino groups, Fe Arylamino group, a methyl group, an ethyl group, tert- butyl group, an alkyl group such as a dodecyl group, a hydroxy group, a carboxy group, and the like.

In general formula (B), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.

The monovalent substituent represented by X ^22, optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, a substituted group An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, and a substituent A good arylthiooxy group, a halogen atom and the like can be mentioned.

  The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl. Group, 2-ethylhexyl group, phenacyl group, and the like.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable. For example, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a terphenyl group, a quarterphenyl group, o-, m-, and p-tolyl groups, xylyl groups, and the like.

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

  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 propyloxy group, an isopropyloxy group, a butoxy group, and a benzyloxy group. .

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, etc. are mentioned.

  The alkylthiooxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms. For example, a methylthiooxy group, an ethylthiooxy group, a propylthiooxy group, an isopropylthiooxy group, a butylthiooxy group Group, isobutylthiooxy group, sec-butylthiooxy group, tert-butylthiooxy group, pentylthiooxy group, isopentylthiooxy group, hexylthiooxy group, heptylthiooxy group, octylthiooxy group, 2-ethylhexyl Examples include a thiooxy group, a decylthiooxy group, a dodecylthiooxy group, an octadecylthiooxy group, and a benzylthiooxy group.

  The arylthiooxy group which may have a substituent is preferably an arylthiooxy group having 6 to 30 carbon atoms, such as a phenylthiooxy group, a 1-naphthylthiooxy group, a 2-naphthylthiooxy group, 2 -Chlorophenylthiooxy group, 2-methylphenylthiooxy group, 2-methoxyphenylthiooxy group, 2-butoxyphenylthiooxy group, 3-chlorophenylthiooxy group, 3-trifluoromethylphenylthiooxy group, 3-cyano Phenylthiooxy group, 3-nitrophenylthiooxy group, 4-fluorophenylthiooxy group, 4-cyanophenylthiooxy group, 4-methoxyphenylthiooxy group, 4-dimethylaminophenylthiooxy group, 4-methylsulfanyl Phenylthiooxy group, 4-phenylsulfanylphenyl There is thiooxyacids group, and the like.

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

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

  Examples of the amide group which may have a substituent on N include N, N-dimethylamide group and N, N-diethylamide group.

Among these, X ²² has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio which may have a substituent Oxy group, arylthiooxy group which may have a substituent, halogenated alkyl group which may have a substituent, amino group which may have a substituent, or a substituent on N A good amide group is preferable, and an alkyl group which may have a substituent is more preferable.

Moreover, although n in general formula (B) represents the integer of 0-5, the integer of 0-3 is preferable from a viewpoint of the ease of a synthesis | combination, and the integer of 0-2 is more preferable.
In Formula ^{(B), if X 22} there are a plurality, the plurality of ^{X 22} may be the same,
May be different.

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

  The compound represented by the general formula (B) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970), and particularly, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  Examples of hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Various compounds described in the specification, specifically 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′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5'-tetraphenyl Imidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  A photoinitiator can be used 1 type or in combination of 2 or more types. When two or more kinds are used, a plurality of compounds represented by the general formula (B) may be used, or a plurality of compounds represented by the general formula (II) may be used. In addition, at least one of the compounds represented by the general formulas (II) and (III) may be used. In addition, at least one compound represented by the general formulas (II) and (III) and an oxime compound other than the compounds represented by the general formulas (II) and (III) or photopolymerization other than the oxime compound are started. An agent may be used. Moreover, you may use a sensitizer together.

  The total content of the photopolymerization initiator is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 20% by mass with respect to the total solid content in the colored photosensitive composition. More preferably, 1% by mass to 10% by mass is most preferable. Within this range, the sensitivity during exposure is high and the color characteristics are also good.

<(E) Alkali-soluble binder>
In the colored photosensitive composition of the present invention, it is preferable to use an alkali-soluble binder in order to improve the film-forming property and from the viewpoint of pattern-forming property.
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  In addition to those described above, the alkali-soluble binder includes, for example, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

  The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the above-mentioned polymer containing a polymerizable group include: Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Manufactured by Diamond Shamrock Co. Ltd.), Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, the Photomer 6173, and the KS resist-106. Cyclomer P series and the like are preferable.

Alkali-soluble binder, developability, from the viewpoint of liquid viscosity, weight average molecular weight (measured in terms of polystyrene by GPC method) is preferably a polymer of 1,000 to 2 × 10 ^5, the weight of the 2000-1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable. It can be used alone or in combination of two or more.

<Other ingredients>
In the colored photosensitive composition of the present invention, if necessary, as long as the effects of the present invention are not impaired, known additives such as polyfunctional thiol compounds, chain transfer agents, polymerization inhibitors, organic solvents, A surfactant, an adhesion improving agent, a crosslinking agent, a development accelerator, and other additives can be contained.
Below, these components are demonstrated.

(Polyfunctional 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 increase sensitivity and suppress ion elution caused by a coloring material such as a dye, so that the colored photosensitive composition of the present invention can be used for producing a color filter of a liquid crystal display device. When the composition is used, it is possible to prevent deterioration of image quality such as crosstalk and display a clear image with high image quality.

  In the present invention, the “polyfunctional thiol compound” means a compound having two or more thiol groups in the molecule. As the polyfunctional thiol compound, a low molecular compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1500 is preferable, and 150 to 1000 is more preferable. The polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, and more preferably 2 to 6 thiol groups. In addition, these compounds are preferably used as a system that is used auxiliary when the radical polymerizable monomer is polymerized. Specifically, the addition amount of the polyfunctional thiol compound is 1 to 20% by mass relative to the total solid content of the composition, or less than the addition amount of the radical polymerizable monomer contained at the same time. It is preferable to make it an addition amount.

  Specific examples of the polyfunctional thiol compound that can be used in the present invention include, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercapto). Propionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Multifunctional thiols, such as trione, etc. And the like as compounds.

  The content of the polyfunctional thiol compound is preferably 0.01 to 20% by mass and more preferably 0.1 to 10% by mass with respect to the total solid content in the colored 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, the pixel adhesion in the obtained color filter is good, and there is no pattern defect. When used in a liquid crystal display device, a colored photosensitive composition having good electrical characteristics can be provided.

(Sensitizer)
A sensitizer can also be added to the colored photosensitive composition of the present invention. Typical sensitizers used in the present invention include those disclosed in Crivello [JVCrivello, Adv. In Polymer Sci, 62, 1 (1984)], specifically 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 to 200% by mass with respect to the photopolymerization initiator.

(Chain transfer agent)
A chain transfer agent may be added to the colored photosensitive composition of the present invention. Examples of the chain transfer agent used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercapto. And mercapto compounds having a heterocyclic ring such as benzimidazole and N-phenylmercaptobenzimidazole.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
The addition amount of the chain transfer agent is preferably in the range of 0.01 to 15% by mass with respect to the total solid content of the colored photosensitive composition of the present invention, from the viewpoint of reducing sensitivity variation. 1-10 mass% is more preferable, and 0.5-5 mass% is especially preferable.

(Polymerization inhibitor)
The colored photosensitive composition of the present invention may contain a polymerization inhibitor.
A polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to a polymerization initiating species such as a radical generated in a colored photosensitive composition by light or heat. , Electron donation) and the like to deactivate the polymerization initiating species and to prevent unintentional initiation of polymerization. The polymerization inhibitors described in paragraphs 0154 to 0173 of JP 2007-334322 A can be used.
Among these, p-methoxyphenol is preferably exemplified as the polymerization inhibitor.
The content of the polymerization inhibitor in the colored photosensitive composition of the present invention is preferably from 0.0001 to 5% by mass, more preferably from 0.001 to 5% by mass, based on the total mass of the polymerizable compound. 001 to 1% by mass is particularly preferable.

[(F) Organic solvent]
The colored photosensitive composition of the present invention preferably contains (F) an organic solvent.
Moreover, it is preferable that the dispersion composition in this invention contains the (F) organic solvent.
The organic solvent contained in the dispersion composition and the organic solvent contained in the colored photosensitive composition may be the same or different, and the organic solvent contained in the dispersion composition and the organic solvent contained in the colored photosensitive composition are one kind. May be two or more.
(F) The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each of the coexisting components and the coating property when the colored photosensitive composition is used, and particularly, the solubility of the solid content. It is preferable to select them in consideration of applicability and safety.

  (F) Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and methyl lactate. , Ethyl lactate, alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc. )), 3-oxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, Ethyl pyruvate, propyrate pyruvate , Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol 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 ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene and xylene.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-mentioned components, and the solubility and the improvement of the coating surface state when an alkali-soluble binder is included. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, It is a mixed solution composed of two or more selected from cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

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

(Surfactant)
The colored photosensitive composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph 0058 of JP-A-2009-098616, and among these, fluorosurfactants are preferable.
Other surfactants that can be used in the present invention include, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554. F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (above, manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (above, manufactured by Sumitomo 3M), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC -104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Footage 250 (Neos Co., Ltd.).
Further, as the surfactant, the structural unit A and the structural unit B represented by the following formula (W) are included, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent is 1, A copolymer having a molecular weight of 000 or more and 10,000 or less can be given as a preferred example.

(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 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 4 or less, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p represents a numerical value of 10% to 80% by mass. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.

L is preferably a branched alkylene group represented by the following formula (W-2). R ⁵ in Formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. Two or three alkyl groups are more preferred.
The sum (p + q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.
The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants can be used alone or in combination of two or more.
The addition amount of the surfactant in the colored photosensitive composition of the present invention is preferably 0.01 to 2.0% by mass, particularly 0.02 to 1.0% by mass in the total solid content of the colored photosensitive composition. preferable. Within this range, the coatability and the uniformity of the cured film are good.

(Adhesion improver)
The colored photosensitive composition of the present invention may contain an adhesion improving agent.
The adhesion improver improves the adhesion between an inorganic substance serving as a support, for example, a silicon compound such as glass, silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the cured film of the colored photosensitive composition layer. A compound. Specific examples include silane coupling agents. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and among them, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
The content of the adhesion improving agent in the colored photosensitive composition of the present invention is preferably 0.1 to 20% by mass, and more preferably 0.2 to 5% by mass with respect to the total solid content of the colored photosensitive composition. .

(Crosslinking agent)
A supplementary crosslinking agent may be used in the colored photosensitive composition of the present invention to further increase the hardness of the colored layer obtained by curing the colored photosensitive composition.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds are mentioned. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, the description in paragraphs [0134] to [0147] of JP-A No. 2004-295116 can be referred to.

(Development accelerator)
A development accelerator can also be added in order to promote the alkali solubility of the non-exposed region when the colored photosensitive composition layer is exposed and to further improve the developability of the colored photosensitive composition. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.

(Other additives)
If necessary, the colored photosensitive composition of the present invention may further contain various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, antioxidants and the like. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
The colored photosensitive composition of the present invention can contain the light stabilizer described in paragraph [0078] of JP-A No. 2004-295116 and the thermal polymerization inhibitor described in paragraph [0081] of the publication. .

(Preparation method of colored photosensitive composition)
The colored photosensitive composition of the present invention is prepared by mixing the above-described components and optional components as necessary. Preferably, the dispersion composition described above is used as a colorant component, and the above-described components are mixed with optional components as necessary.
In preparing the colored photosensitive composition, the components constituting the colored photosensitive composition may be mixed together or sequentially. In addition, there are no particular restrictions on the charging order and working conditions when blending.
The colored photosensitive composition prepared as described above can preferably be used after being filtered using a filter having a pore size of about 0.01 μm to 3.0 μm.

  Since the colored photosensitive composition of the present invention can form a colored cured film having excellent heat resistance and excellent contrast, it can be used for forming colored pixels such as color filters used in liquid crystal display devices and printing inks. , Ink jet inks, paints and the like can be suitably used.

<< Color filter and manufacturing method thereof >>
The color filter of the present invention is configured by providing a support and a colored region made of the colored photosensitive composition of the present invention on the support. The colored region on the support is composed of colored layers such as red (R), green (G), and blue (B) forming each pixel of the color filter.

The method for producing a color filter of the present invention includes a colored layer forming step (A) in which a colored layer (colored photosensitive composition layer) is formed by applying the above-described colored photosensitive composition on a support, and a step ( The exposure process (B) which carries out pattern-like exposure with respect to the colored layer formed in A), and the image development process (C) which develops the said exposed colored layer and forms a colored pattern are included.
Moreover, in the manufacturing method of the color filter of this invention, the aspect which further provided the process (D) which heat-processes with respect to the coloring pattern obtained at the process (C) is preferable.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.

-Process (A)-
In the method for producing a color filter of the present invention, first, the above-described colored photosensitive composition of the present invention is applied onto a support by spin coating, slit coating, cast coating, roll coating, bar coating, ink jet or the like coating method. Is applied to form a colored layer, and then the colored layer is dried by heating (pre-baking) or vacuum drying.

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

Examples of the pre-baking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
Moreover, the thickness of the colored layer formed with a colored photosensitive composition is suitably selected according to the objective. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, and the range of 1.0 μm to 4.0 μm is more preferable. In addition, the thickness of a colored layer is a film thickness after drying.

-Process (B)-
Subsequently, in the method for producing a color filter of the present invention, pattern-like exposure is performed on the colored layer formed on the support. As light or radiation applicable to exposure, g-line, h-line, i-line and various laser beams are preferable, and i-line is particularly preferable. When using a high pressure mercury lamp in the irradiation light is ^preferably irradiated at an exposure dose of ^{5mJ / cm 2 ~500mJ / cm 2} .

  In addition, as other exposure light sources, ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser light sources, and the like can be used.

~ Exposure process using laser light source ~
In the exposure method using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength range of 300 nm to 410 nm, and more preferably a wavelength of 300 nm to 360 nm. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. . The pattern exposure, from the viewpoint of ^{productivity,} preferably in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable.

  There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), and DF2200G (Dainippon Screen) can be used. is there. Further, devices other than those described above are also preferably used.

-Step (C)-
Subsequently, the colored layer after exposure is developed with a developer. Thereby, a colored pattern can be formed. As long as the developing solution dissolves the uncured portion of the colored layer and does not dissolve the cured portion, a combination of various organic solvents or an alkaline aqueous solution can be used. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 10-13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Examples include alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene.
The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 23 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.
Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean 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 colored pattern (pixel) formed using a colored photosensitive composition.

-Process (D)-
It is preferable to further heat-treat the colored pattern after development or the colored pattern subjected to post-exposure by ultraviolet irradiation as described above. By heating the formed color pattern (so-called post-bake process), the color pattern can be further cured. This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a blue pixel in the color filter. In manufacturing a color filter having a plurality of hue pixels, the above-described step (A), step (B), step (C), and step (D) may be repeated according to the desired number of colors.
In addition, whenever formation, exposure, and development of a single color layer are completed (for each color), the step (D) may be performed, or formation, exposure, and formation of all colored layers having a desired number of colors. After the development is completed, the step (D) may be performed collectively.
In addition, the colored photosensitive composition of the present invention can form a blue colored layer and provide a blue pixel on the support, but when the colored pixel is composed of red, blue and green, the order of providing the colored layer is , Any order.

<< Display device >>
The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in heat resistance and contrast because it uses the colored photosensitive composition of the present invention.
The display device of the present invention includes the color filter of the present invention.
Specifically, as a display device of the present invention, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone. Display devices such as digital camera display devices and car navigation display devices, particularly color display devices are suitable.
When the color filter of the present invention is used in an organic EL display device, a liquid crystal display device or the like, an image having excellent spectral characteristics and contrast can be displayed while achieving a good hue.

<Liquid crystal display device>
A liquid crystal display device using the color filter of the present invention will be described. For the definition of organic EL display devices and liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho (issued in 1989) ”. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

  The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can. The color filter of the present invention can also be used for a COA (Color-filter On Array) system.

  When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, but further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

[Example 1]
-Preparation of blue dispersion composition 1-
<Preparation of coloring material composition>
Commercially available C.I. I. Pigment Blue 15: 6 (product name: FASTGEN BLUE EP193 manufactured by DIC Corporation), 100 parts of a dye (exemplary compound 1 of the dye), 400 parts of sodium chloride, and 140 parts of a water-soluble organic solvent diethylene glycol (table type kneader) (Made by Irie Shokai Co., Ltd.) and kneaded for 10 hours. Next, this kneaded product was stirred and mixed with water using a dissolver (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then filtered and washed repeatedly to remove sodium chloride and the solvent to obtain a water cake of a coloring material. Thereafter, the water cake was dried in an oven at 80 ° C. for 6 hours. I. Pigment Blue 15: 6 and a dye coloring material composition were obtained.

<Coarse dispersion>
After blending with the following composition using the above color material composition, the mixture was dispersed using Eiger mill (manufactured by Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.8 mm.
Colorant composition: 150 parts Pigment derivative (I) (the following structure): 10 parts Polymer dispersant (exemplary compound 1 below): 80 parts Propylene glycol monomethyl ether acetate: 260 parts Pigment derivative ( I) was synthesized according to the method described in paragraph 0056 of JP2003-253078A. CuPc in the following structural formula represents a copper phthalocyanine residue. Exemplary compound 1 was synthesized according to the method described in JP2011-178865A.

Pigment derivative (I)

<Precise dispersion>
The dispersion after the coarse dispersion was taken out, and 30 parts of propylene glycol monomethyl ether acetate was added to 100 parts of the dispersion and mixed. Then, it disperse | distributed using the Eiger mill (Eiger Japan Co., Ltd. product) and the zirconia bead of diameter 0.1mm.
<Density adjustment>
The dispersion after precision dispersion was taken out, and diluted with propylene glycol monomethyl ether acetate so that the pigment concentration was 10%, whereby blue dispersion composition 1 was obtained.

-Preparation of colored photosensitive composition-
The following components were mixed and dissolved to prepare a colored photosensitive composition 1.
-Organic solvent 1: 33 parts of propylene glycol monomethyl ether acetate-Organic solvent 2: 26 parts of diethylene glycol ethyl methyl ether-Alkali-soluble binder 1: Methacrylic acid in cyclohexyl methacrylate / methacrylic acid / glycidyl methacrylate (= molar ratio: 30/30/40) 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 26800) 4 parts, polymerizable compound 1: Japan KAYARAD DPHA 3 parts, polymerizable compound 2: Toa Gosei Co., Ltd., Aronix TO-2349 3 parts, polymerization inhibitor: p-methoxyphenol 0.003 part, photopolymerization initiator 1: 1- (O-A Tiloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone 0.3 part-photopolymerization initiator 2: 1,3-dihydro-1-phenyl-2H-benzimidazole -2-thione) 0.2 part, polyfunctional thiol compound: 1,4-bis (3-mercaptobutyryloxy) butane 0.1 part, adhesion improver: 3-methacryloxypropyltrimethoxysilane) 0.2 Parts · Fluorosurfactant: DIC Corporation MegaFuck F-554 (0.2% propylene glycol monomethyl ether acetate solution) 5 parts · Blue dispersion composition 1 30 parts

[Examples 2 to 6]
In Example 1, colored photosensitive compositions 2 to 6 were prepared in the same manner as in Example 1 except that the dye used when preparing the color material composition was changed as shown in Table 1.

Example 7
-Preparation of blue dispersion composition 7-
<Miniaturization of pigment>
Commercially available C.I. used in Example 1 I. Pigment Blue 15: 6 100 parts, 400 parts of sodium chloride, and 140 parts of diethylene glycol were charged into a table type kneader (manufactured by Irie Shokai Co., Ltd.) and kneaded for 10 hours. Next, this kneaded product was stirred and mixed with water using a dissolver (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then filtered and washed repeatedly to remove sodium chloride and the solvent to obtain a water cake of a coloring material. Thereafter, the water cake was dried in an oven at 80 ° C. for 6 hours. I. Pigment Blue 15: 6 refined pigment was obtained.

<Coarse dispersion>
Using the above-mentioned fine pigment, the following composition was prepared, and the mixture was dispersed using Eiger mill (manufactured by Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.8 mm.
-Refined pigment 100 parts-Dye: Exemplified 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 dispersion after the coarse dispersion was taken out, and then dispersed using Eiger mill (manufactured by Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.1 mm.
<Density adjustment>
The dispersion after the fine dispersion was taken out and diluted by adding propylene glycol monomethyl ether acetate so that the pigment concentration was 10% to obtain a blue dispersion composition 7.
-Preparation of colored photosensitive composition 7-
A 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 in Example 1.

[Examples 8 to 12]
In Example 7, colored photosensitive compositions 8 to 12 were prepared in the same manner as in Example 7 except that the dye added by coarse dispersion was changed as shown in Table 1.

Example 13
-Preparation of blue dispersion composition 13-
<Miniaturization of pigment>
Commercially available C.I. used in Example 1 I. Pigment Blue 15: 6 100 parts, 400 parts of sodium chloride, and 140 parts of diethylene glycol were charged into a table type kneader (manufactured by Irie Shokai Co., Ltd.) and kneaded for 10 hours. Next, this kneaded product was stirred and mixed with water using a dissolver (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then filtered and washed repeatedly to remove sodium chloride and the solvent to obtain a water cake of a coloring material. Thereafter, the water cake was dried in an oven at 80 ° C. for 6 hours. I. Pigment Blue 15: 6 refined pigment was obtained.
<Coarse dispersion>
Using the above-mentioned fine pigment, the following composition was prepared, and the mixture was dispersed using Eiger mill (manufactured by Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.8 mm. At that time, the finely divided pigment and the dye were first mixed in a powder state, and then other materials were added and dispersed.
-Fine pigment 100 parts-Dye: 50 parts of dye exemplified compound 1-10 parts of pigment derivative (I)-Polymer dispersant: 80 parts of exemplified compound 1-260 parts of propylene glycol monomethyl ether acetate

<Precise dispersion>
The dispersion after the coarse dispersion was taken out, and 30 parts of propylene glycol monomethyl ether acetate was added to 100 parts of the dispersion and mixed. Then, it disperse | distributed using the Eiger mill (Eiger Japan Co., Ltd. product) and the zirconia bead of diameter 0.1mm.
<Density adjustment>
The dispersion composition after the fine dispersion was taken out and diluted by adding propylene glycol monomethyl ether acetate so that the pigment concentration was 10% to obtain a blue dispersion composition 13.

-Preparation of colored photosensitive composition 13-
A 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 in Example 1.

[Examples 14 to 18]
In Example 13, colored photosensitive compositions 14 to 18 were prepared in the same manner as in Example 13 except that the dye added by coarse dispersion was changed as shown in Table 1.

Example 19
-Preparation of blue dispersion composition 19-
<Miniaturization of pigment>
Commercially available C.I. used in Example 1 I. Pigment Blue 15: 6 100 parts, sodium chloride 400 parts, and diethylene glycol 140 parts were charged in a table type kneader (manufactured by Irie Shokai Co., Ltd.) and kneaded for 10 hours. Next, this kneaded product was stirred and mixed with water using a dissolver (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then filtered and washed repeatedly to remove sodium chloride and the solvent to obtain a water cake of a coloring material. Thereafter, the water cake was dried in an oven at 80 ° C. for 6 hours. I. Pigment Blue 15: 6 refined pigment was obtained.
<Coarse dispersion>
Using the above-mentioned fine pigment, the following composition was prepared, and the mixture was dispersed using Eiger mill (manufactured by Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.8 mm.
-Refined pigment 100 parts-Pigment derivative (I) 10 parts-Polymer dispersant: 80 parts of Exemplified Compound 1-260 parts of propylene glycol monomethyl ether acetate

<Precise dispersion>
The dispersion after the coarse dispersion was taken out, and 11 parts of Exemplified Compound 1 of a dye was further added to 100 parts of the dispersion and mixed. Thereafter, 30 parts of propylene glycol monomethyl ether acetate was added and dispersed using Eiger mill (manufactured by Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.1 mm.
<Density adjustment>
The dispersion composition after the fine dispersion was taken out, diluted with propylene glycol monomethyl ether acetate so that the pigment concentration was 10%, and the blue dispersion composition 19 was obtained.

-Preparation of colored photosensitive composition 19-
A 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 in Example 1.

[Examples 20 to 24]
In Example 19, colored photosensitive compositions 20 to 24 were prepared in the same manner as in Example 19 except that the dye added during precision dispersion was changed as shown in Table 1.

[Comparative Example 1]
-Preparation of blue dispersion composition A-
<Miniaturization of pigment>
Commercially available C.I. used in Example 1 I. Pigment Blue 15: 6 100 parts, 400 parts of sodium chloride, and 140 parts of diethylene glycol were charged into a table type kneader (manufactured by Irie Shokai Co., Ltd.) and kneaded for 10 hours. Next, this kneaded product was stirred and mixed with water using a dissolver (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then filtered and washed repeatedly to remove sodium chloride and the solvent to obtain a water cake of a coloring material. Thereafter, the water cake was dried in an oven at 80 ° C. for 6 hours. I. Pigment Blue 15: 6 refined pigment was obtained.
<Coarse dispersion>
Using the above-mentioned fine pigment, the following composition was prepared, and the mixture was dispersed using Eiger mill (manufactured by Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.8 mm.
-Fine pigment 100 parts-Pigment derivative (I) 10 parts-Polymeric dispersant: 80 parts of Exemplified Compound 1-260 parts propylene glycol monomethyl ether acetate <Precise dispersion>
The dispersion after the coarse dispersion was taken out, and 100 parts of the dispersion was mixed with 125 parts of Exemplified Compound 1 (9% solution of propylene glycol monomethyl ether acetate). Thereafter, the mixture was dispersed using Eiger mill (manufactured by Eiger Japan Co., Ltd.) 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 colored photosensitive composition A-
A 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 in Example 1.

[Comparative Example 2]
-Preparation of blue dispersion composition B-
<Miniaturization of pigment>
Commercially available C.I. used in Example 1 I. Pigment Blue 15: 6 100 parts, sodium chloride 400 parts, and diethylene glycol 140 parts were charged in a table type kneader (manufactured by Irie Shokai Co., Ltd.) and kneaded for 10 hours. Next, this kneaded product was stirred and mixed with water using a dissolver (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then filtered and washed repeatedly to remove sodium chloride and the solvent to obtain a water cake of a coloring material. Thereafter, the water cake was dried in an oven at 80 ° C. for 6 hours. I. Pigment Blue 15: 6 was obtained.
<Coarse dispersion>
Using the above-mentioned fine pigment, the following composition was prepared, and the mixture was dispersed using Eiger mill (manufactured by Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.8 mm.
-Fine pigment 100 parts-Pigment derivative (I) 10 parts described in JP-A-2011-178865-Polymer dispersant (Exemplary Compound A) 80 parts-Propylene glycol monomethyl ether acetate 260 parts <Precise dispersion>
The dispersion after the coarse dispersion was taken out, and 19 parts of propylene glycol monomethyl ether acetate was added to 100 parts of the dispersion and mixed. Then, it disperse | distributed using the Eiger mill (Eiger Japan Co., Ltd. product) and the zirconia bead of diameter 0.1mm. After dispersion, 11 parts of a dye (Dye Exemplified Compound 1) was added and mixed with a three-one motor to obtain a blue dispersion composition B.
-Preparation of colored photosensitive composition B-
A 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 in Example 1.

[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. used in Example 1. I. Pigment Blue 15: 6 100 parts Dye exemplified compound 1 50 parts Pigment derivative (I) 10 parts Polymer dispersing agent (exemplary compound 1) 80 parts Propylene glycol monomethyl ether acetate 760 parts-Colored photosensitive composition C Preparation of
A 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 in Example 1.

Ci and Cf in the colored photosensitive composition thus prepared are shown below.
Ci in Examples 1 to 6 is calculated from the concentration of the specific dye at the time of premixing, and all are 33.3%, and Cf is the concentration of the dye in the dispersion composition after concentration adjustment after dispersion is completed. In Examples 1 to 6, all are 5.0%.
Ci in Examples 7 to 18 is calculated from the composition of coarse dispersion. The Cis of Examples 7 to 12 are all 5.5%, and the Cis of Examples 13 to 18 are all 10%. Cf is calculated from the concentration of the dye in the dispersion composition after concentration adjustment after completion of dispersion, and in Examples 7 to 18, all are 5.0%.
In Examples 19 to 24, Ci is calculated from the composition of the fine dispersion, all are 7.8%, and Cf is calculated from the concentration of the dye in the dispersion composition after concentration adjustment after the dispersion is completed. Both are 5.0%.
In Comparative Examples 1 to 3, all are Ci = Cf, and both are 5.0%.

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

-Formation of colored photosensitive composition layer (colored layer)-
After applying the colored photosensitive composition prepared above on a glass (# 1737; Corning) substrate by spin coating, the volatile components are volatilized by drying at room temperature for 30 minutes to form a colored layer. did. This colored layer was irradiated with i-line (wavelength 365 nm) through a fine line pattern mask to form a latent image. An ultra-high pressure mercury lamp was used as the i-line light source, and it was irradiated as parallel light. At this time, the irradiation light quantity was 40 mJ / cm ² . Next, the colored layer on which the latent image was formed was developed with an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%) at 26 ° C. for 45 seconds, and then rinsed with running water for 20 seconds. And dried with a spray to obtain a fine line pattern image. The obtained fine line pattern image was post-baked at 230 ° C. for 20 minutes to obtain a colored layer having a blue fine line pattern with a thickness of 2 μm.

(Contrast evaluation)
When the obtained substrate having the colored layer is sandwiched between two polarizing films, the luminance value in the case where the polarizing axes of the two polarizing films are parallel and perpendicular is measured by a color luminance meter (manufactured by Topcon Corporation). , Model number: BM-5A), the brightness when the polarization axes of the two polarizing films were parallel was divided by the brightness when vertical, and the obtained value was obtained as contrast. 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 colored layer obtained above was measured using a microspectrophotometer (manufactured by Olympus Corporation, model number OSP-SP200). From the obtained transmission spectrum, the chromaticity coordinate x value, y value, and Y value in the CIE 1931 color system were determined.
It can be said that the spectral characteristic is more excellent as the Y value at (x, y) = (0.138, 0.085) is larger.

(Heat-resistant)
After measuring the transmission spectrum of the colored layer obtained above using a microspectrophotometer (model number OSP-SP200, manufactured by Olympus Corporation), additional baking was performed at 230 ° C. for 60 minutes, and the transmission spectrum was evaluated again. . The Y value difference (ΔY) before and after the additional baking was calculated and used as an index of heat resistance. It can be said that the smaller the ΔY, the better the heat resistance.

(Dye adsorption rate)
Each blue dispersion composition was centrifuged at 50000 rpm with an ultracentrifuge (manufactured by Hitachi Koki Co., Ltd.) to obtain a supernatant containing free components. The amount of dye in the supernatant was evaluated by HPLC, and the adsorption rate (%) was defined by the following formula.

From the results in Table 1, the following can be said. The colored photosensitive compositions 1 to 24 of the present invention have excellent heat resistance with respect to the colored photosensitive compositions A to C of the comparative examples. Since heat resistance correlates with the dye adsorption rate, it is presumed that thermal fading is suppressed by the adsorption of the dye to the pigment. Since the dispersion composition of the present invention has a high dye adsorption rate, it is easy to obtain high heat resistance.
This is considered due to the fact that the dye concentration Ci when the dye is added is higher than the dye concentration Cf in the final dispersion composition when preparing the dispersion composition in the present invention. That is, it is considered that adsorption to the pigment is likely to occur by adding the dye at a higher concentration (for example, inputting the dye in the solid state at the time of pigment miniaturization as described in Example 1).

As shown in the comparative example, when the dye is in a low concentration (Comparative Example 1) even when charged in the dispersion step, or when the mixture is simply stirred and mixed after the dispersion step (Comparative Example 2), the dispersion is sufficient. Therefore, when the pigment is not sufficiently crushed and the particle surface area is small (Comparative Example 3), the dye adsorption rate is low, and thus the heat resistance is also low.
Surprisingly, the colored photosensitive compositions 1 to 24 of the present invention had an excellent contrast as compared with the colored photosensitive compositions A to C of the comparative examples. The reason for this is not sufficiently clear, but it is thought that the aggregation of the dye during the colored layer formation process was suppressed because the dye adsorbed on the pigment surface and the amount of free dye in the dispersion composition was small. . By suppressing the aggregation of the dye, the particles in the colored layer that cause light scattering are reduced, and it is estimated 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 the display characteristics were evaluated.

<Preparation of red colored photosensitive composition R>
The following red pigment dispersion composition was mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. For 3 hours. The mixed solution thus obtained was further subjected to a dispersion treatment for 12 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO-3000-10 with a decompression mechanism. (Nippon BEE Co., Ltd.) was used, and the dispersion process was performed 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. I. Pigment Red 177 50 parts benzyl methacrylate / methacrylic acid copolymer 70 parts (copolymerization composition ratio 70/30, weight average molecular weight 30000, acid value 40)
・ Propylene glycol monomethyl ether acetate 800 parts

Components of the following composition were further added to the obtained pigment dispersion to prepare a red colored photosensitive composition R.
[Red colored photosensitive composition R composition]
・ 100 parts of the above red pigment dispersion ・ Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (Mw: 30,000) (solid content 50%) 12 parts Polymerizable compound 1: Nippon Kayaku Co., Ltd., KAYARAD DPHA 12.1 parts, photopolymerization initiator: 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer) 3.1 parts, sensitized Dye: 4,4'-bis (diethylamino) benzophenone 4.2 parts, hydrogen donating compound: 2-mercaptobenzothiazole 2.1 parts, polymerization inhibitor: p-methoxyphenol 0.001 part, fluorine-based surfactant (Product name: Megafac R08 manufactured by DIC Corporation) 0.5 parts / Propylene glycol monomethyl ether acetate 60 parts

<Preparation of green colored photosensitive composition G>
In preparation of the red colored photosensitive composition R, C.I. I. Pigment Red 254 instead of C.I. I. Pigment Green 58 (103 copies), C.I. I. Pigment Red 177 instead of C.I. I. A green colored photosensitive composition G was produced in the same manner except that 19 parts of Pigment Yellow 150 was used.

<Preparation of black colored photosensitive composition K>
The pigment dispersion composition was changed to the following composition, and a black pigment dispersion was prepared by carrying out a dispersion treatment in the same manner as the preparation of the red pigment dispersion.
[Black pigment dispersion composition]
Carbon black: Trade name: Nexex 35, 13.1 part manufactured by Degussa Japan Co., Ltd. Polymer: benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer (molecular weight 37,000) 6.7 parts 79.1 parts propylene glycol monomethyl ether acetate, 0.65 parts dispersant (the following compound)

Using the obtained black pigment dispersion composition, a black colored photosensitive composition K was prepared with the following composition.
[Black-colored photosensitive composition K composition]
-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) 27 parts 9.1 parts of a mixture of propylene glycol monomethyl ether acetate and polymerization inhibitor: 0.002 part of hydroquinone monomethyl ether, polymerizable compound: KAYARAD DPHA 12 parts manufactured by Nippon Kayaku Co., Ltd., polymerization initiator: 2,4-bis 0.16 parts of (trichloroethyl) -6- [4 ′ (N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine / 30% solution of surfactant (the following compound) in methyl ethyl ketone 0 .042 parts

<Production of color filter>
<Formation of black matrix>
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned 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.
The black colored photosensitive resin composition K was applied on a glass substrate coater (manufactured by FAS Asia, trade name: MH-1600) having a slit-like nozzle on the substrate. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm black photosensitive composition layer was obtained.
In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the photosensitive film The distance between the conductive resin layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .

  Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the black photosensitive composition layer, and then a KOH-based developer (KOH, containing a nonionic surfactant, trade name: CDK-1, (Fujifilm Electronics Materials Co., Ltd.) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove residues. Finally, heat treatment was performed at 220 ° C. for 30 minutes to form a black matrix.

<Formation of RGB pixels>
The red colored photosensitive composition R, the green colored photosensitive composition G, and the blue photosensitive composition prepared in Example 1 were sequentially applied to the glass substrate on which the black matrix was formed, in the same process as when the black matrix was formed. Then, lamination and patterning were performed to obtain a color filter of RGB three-color pixels. At this time, the thickness of the colored portion of each color of RGB was 1.6 μm.

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

<Spacer formation>
A spacer was formed on the ITO transparent electrode prepared above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.

<Formation of projection for controlling liquid crystal alignment>
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal alignment control projection on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display substrate.

[Coating liquid formulation for positive photosensitive resin layer]
・ Positive resist solution (FH-2413F manufactured by Fujifilm Electronics Materials Co., Ltd.) 53.0 parts ・ Methyl ethyl ketone 46.5 parts ・ Megafac F-780F (manufactured by DIC Corporation) 0.05 parts

<Production of liquid crystal display device>
An alignment film made of polyimide was further provided on the liquid crystal display device substrate obtained above. After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant.
A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, an LED light source (a liquid crystal television manufactured by SONY, a backlight light source of KDL-40ZX1) was disposed as a light source on the side of the liquid crystal cell provided with the polarizing plate, thereby obtaining a liquid crystal display (LCD).

  The liquid crystal display device produced as described above has high contrast and brightness, and is suitable as a display device. In this example, the MVA mode liquid crystal display device was evaluated. However, the color effect composition of the present invention can be used for a liquid crystal display device of another mode or a color filter of an organic EL display. It seems that good image quality can be obtained as well.

Claims (10)

(A) a blue pigment, and (B) a dye having a different mother skeleton from the blue pigment, wherein the dye is a metal complex in which the structure represented by the following general formula (I) is coordinated to a metal atom or a metal compound A compound and one or more dyes selected from triphenylmethane- based dyes, and (C) a polymerizable compound, wherein 15% by mass or more of the (B) dye is the (A) blue pigment. A colored photosensitive composition adsorbed on the surface.


In general 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, halogen, An atom, an alkyl group, an aryl group, or a heterocyclic group is represented.   The colored photosensitive composition according to claim 1, comprising a dispersion composition obtained by dispersing the (A) blue pigment and the (B) dye in the same system.   In the dispersion composition, the concentration of the dye (B) in the dispersion composition in the initial stage of dispersion is Ci, and after the dispersion is completed, the dispersion composition after concentration adjustment for preparing a colored photosensitive composition is used. The colored photosensitive composition according to claim 2, which is a dispersion composition satisfying a relationship of Ci> Cf when the concentration of the (B) dye is Cf.   The (A) blue pigment is Cl of PB 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79. The colored photosensitive composition according to any one of claims 1 to 3, which is at least one selected from the group wherein 80 is changed to OH and 80.   5. The dispersion composition according to claim 1, comprising a dispersion composition obtained by premixing the (A) blue pigment and the (B) dye and then dispersing the resulting color material composition. The colored photosensitive composition described in 1.   Furthermore, the coloring photosensitive composition of any one of Claims 1-5 containing (D) photoinitiator.   Furthermore, (E) The coloring photosensitive composition of any one of Claims 1-6 containing an alkali-soluble binder.   The color filter produced using the coloring photosensitive composition of any one of Claims 1-7. A colored layer forming step of forming the colored layer by applying the colored photosensitive composition according to any one of claims 1 to 7 on a support;
An exposure step of exposing the formed colored layer in a pattern-like manner;
A development step of developing the colored layer after exposure to form a colored pattern;
The manufacturing method of the color filter which has this.   A display device comprising the color filter according to claim 8 or the color filter obtained by the manufacturing method according to claim 9.