JP2019105727A - Color filter coloring agent, coloring composition, and color filter - Google Patents

Abstract

To provide aluminum phthalocyanine that is excellent in fastness (heat resistance, light resistance, and solvent resistance) and that realizes excellent color characteristics (lightness and tinctorial power) and contrast ratio when used for a color filter or the like.SOLUTION: A color filter coloring agent is aluminum phthalocyanine represented by general formula (1) whose x-ray diffraction pattern using the CuKα ray has peaks at diffraction angle 2θ(±0.2)=6.8°, 11.4°, 15.8°, 23.8°and 24.9°.SELECTED DRAWING: Figure 1

Description

  Embodiments of the present invention relate to novel color filter colorants. Another embodiment relates to a coloring composition containing the above-mentioned aluminum phthalocyanine and a color filter formed from the above-mentioned coloring composition. The color filter can be suitably used for a color liquid crystal display device, an organic EL display device, a color image pickup tube element and the like.

  In recent years, materials for forming color images, in particular, have become mainstream as image recording materials. Specifically, ink jet recording materials, thermal transfer recording materials, electrophotographic recording materials, transfer type silver halide photosensitive materials, printing inks, recording pens, etc. are actively used as color image recording materials. ing. In addition, color filters are used to record and reproduce color images in imaging devices such as CCDs in photographing equipment and in LCDs, PDPs, organic electroluminescence, and electronic paper (electronic paper) in displays. In these color image recording materials and color filters, dyes (dyes and pigments) of the three primary colors of so-called additive color mixing method and subtractive color mixing method are used to display or record a full color image. However, the fact is that there is no dye that has absorption characteristics and color characteristics that can realize a preferable color reproduction range and that is compatible with various usage conditions, and improvement is strongly desired.

  The dyes used in each of the above applications differ in the color characteristics required by the application and the required quality for each application, but pigments are mainly used as dyes from the viewpoint of the light resistance and heat resistance of the recorded matter. ing. For example, in a color filter application, C.I. I. Pigment Green 36 and 58 are used.

  It is common to use various phthalocyanine type compounds as a coloring agent for manufacture of the green filter in a color filter, and many compositions for color filters containing these are proposed. Among them, many colorants for color filters using a copper phthalocyanine compound or a zinc phthalocyanine compound have been proposed.

  Patent Document 1 proposes a composition for a color filter using a halogenated phthalocyanine compound substituted with at least four halogen atoms as a green colorant.

  According to Patent Document 2, as a green pigment, a halogenated copper phthalocyanine pigment and a central metal are selected from the group consisting of Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn. A composition for a color filter is proposed which comprises a green colorant consisting of at least one halogenated foreign metal phthalocyanine pigment.

  Each of these phthalocyanine compounds is a material for producing a high brightness color filter. However, in recent years, along with the demand for high lightness, the demand for items such as wide color reproduction and high tinting power has also become high, and in the composition using these proposed colorants, the balance between lightness and tinting power is insufficient Met.

  Patent Document 3 discloses a pigment composition maintaining sharp hue, high light resistance and high heat resistance by using a blue aluminum phthalocyanine pigment not containing halogen and a green pigment containing halogen. There is.

  Patent Document 4 discloses that, by using an aluminum phthalocyanine pigment as a main pigment in a coloring composition for a green color filter segment, high lightness can be obtained with high chromaticity even with a relatively small content. Color density and color purity Technology that makes the

  In addition to the monomeric aluminum phthalocyanine pigment described in Patent Document 4, a dimerized pigment is also proposed as the aluminum phthalocyanine pigment. In Patent Document 5, an aluminum phthalocyanine pigment is bis (phthalocyanylalumino) tetraphenyldisiloxane pigment which is dimerized with diphenylchlorosilane, or bis (phthalocyanylaluminum) phenyl phosphonate which is dimerized with phenylphosphonic acid. Pigments are disclosed.

  However, the pigment composition containing these aluminum phthalocyanine compounds has a problem that the heat resistance at 230 ° C. or higher, and the light resistance for a long time are not sufficient, and the spectral shape is changed, which is required for color filter applications. was there. Furthermore, at present, the problem of high viscosity of the coloring composition due to poor dispersibility is not sufficiently improved.

Japanese Patent Application Laid-Open No. 2002-131521 JP, 2002-250812, A Unexamined-Japanese-Patent No. 2003-4930 Japanese Patent Application Publication No. 2004-333817 Japanese Patent Application Laid-Open No. 57-90058 JP 2012-155231 A

  The problem to be solved by the present invention is to provide a colorant for a color filter which is excellent in fastness (heat resistance, light resistance, solvent resistance) and is also good in lightness, contrast ratio and coloring power. Also, a coloring composition excellent in fastness (heat resistance, light resistance, solvent resistance) using the above aluminum phthalocyanine, and excellent in lightness, contrast ratio and coloring power when used for a color filter application, and It is to provide a high quality color filter using it.

  As a result of intensive studies to solve the above problems, the present inventors have obtained novel aluminum phthalocyanines, and found that they are excellent in fastness and excellent in color characteristics, according to the present invention. It reached.

That is, the present invention is represented by the following general formula (1), and the X-ray diffraction pattern by CuKα ray has a diffraction angle 2θ (± 0.2) = 6.8 °, 11.4 °, 15.8 °, The present invention relates to a colorant for a color filter, which is an aluminum phthalocyanine having peaks at 23.8 ° and 24.9 °.

(In the general formula (1), Y ₁ represents —OP (= O) R ₁ R ₂ , wherein R ₁ and R ₂ each independently represent an alkoxy group having 1 to 5 carbon atoms.)

  The present invention is also represented by the following general formula (1), and the X-ray diffraction pattern by CuKα ray has a diffraction angle 2θ (± 0.2) = 6.7 °, 11.3 °, 16.6 °, The present invention relates to a colorant for a color filter, which is an aluminum phthalocyanine having a peak at 25.5 °.

(In the general formula (1), Y ₁ represents —OP (= O) R ₁ R ₂ , wherein R ₁ and R ₂ each independently represent an alkoxy group having 1 to 5 carbon atoms.)

  The present invention is also represented by the following general formula (1), and the X-ray diffraction pattern by CuKα ray has a diffraction angle 2θ (± 0.2) = 4.7 °, 6.8 °, 9.6 °, The present invention relates to a colorant for a color filter, which is an aluminum phthalocyanine having peaks at 11.4 °, 15.6 °, and 24.0 °.

(In the general formula (1), Y ₁ represents —OP (= O) R ₁ R ₂ , wherein R ₁ and R ₂ each independently represent an alkoxy group having 1 to 5 carbon atoms.)

  The present invention also relates to a coloring composition comprising a coloring agent, a binder resin and an organic solvent, wherein the coloring agent comprises the coloring agent for color filter.

  The present invention also relates to the coloring composition for color filters, wherein the coloring agent further contains at least one of a green pigment and a yellow pigment.

  In the present invention, the green pigment is C.I. I. Pigment Green 7, 36 and 58, and at least one selected from the group consisting of C.I. I. The coloring composition for color filters is at least one selected from the group consisting of CI Pigment Yellow 138, 139, 150 and 185.

  The present invention also relates to the above-mentioned coloring composition for color filter, which contains at least one of a photopolymerizable monomer and a photopolymerization initiator.

  Also, the present invention provides a color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one green filter segment comprises the coloring composition for the color filter. The present invention relates to a color filter formed by

  According to the present invention, a color filter which is excellent in fastness (heat resistance, light resistance, solvent resistance) by the aluminum phthalocyanine represented by the above general formula (1), and further has good lightness, contrast ratio and coloring power. It is possible to provide a coloring agent. In addition, the coloring composition containing the aluminum phthalocyanine of the present invention as a coloring agent is excellent in fastness (heat resistance, light resistance, solvent resistance), and when used for color filter applications, it has good brightness, contrast ratio and coloring power. An excellent high quality color filter can be provided.

FIG. 1 is an X-ray diffraction pattern of the aluminum phthalocyanine (P-1) produced in Example 1 by CuKα rays. FIG. 2 is an X-ray diffraction pattern of the aluminum phthalocyanine (P-2) produced in Example 2 by CuKα rays. FIG. 3 is an X-ray diffraction pattern of the aluminum phthalocyanine (P-3) produced in Example 3 by CuKα rays.

Hereinafter, the present invention will be described in detail.
In the present specification, when “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid”, “(meth) acrylate” or “(meth) acrylamide” is described, it is particularly described Unless there is any, respectively, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide" Represent. Further, in the present specification, "CI" means color index (CI).

<Aluminum phthalocyanine>
The aluminum phthalocyanine of the present invention has the following specific X-ray diffraction pattern, is represented by the general formula (1), and can be suitably used as a colorant used in a coloring composition, in particular as a green colorant.

(In the general formula (1), Y ₁ represents —OP (= O) R ₁ R ₂ , wherein R ₁ and R ₂ each independently represent an alkoxy group having 1 to 5 carbon atoms.)

The aluminum phthalocyanine represented by General formula (1) of this invention can take several preferable crystal forms as follows.
-An aluminum phthalocyanine having an X-ray diffraction pattern with CuKα rays having a diffraction angle 2θ (± 0.2) = 6.8 °, 11.4 °, 15.8 °, 23.8 °, 24.9 ° (Hereafter, it is abbreviated as aluminum phthalocyanine (A)).
An aluminum phthalocyanine having an X-ray diffraction pattern with CuKα rays having peaks at diffraction angles 2θ (± 0.2) = 6.7 °, 11.3 °, 16.6 °, 25.5 ° (hereinafter aluminum phthalocyanine) (Abbreviated as (B)).
The X-ray diffraction pattern by the CuKα ray has a diffraction angle 2θ (± 0.2) = 4.7 °, 6.8 °, 9.6 °, 11.4 °, 15.6 °, 24.0 ° Aluminum phthalocyanine having a peak (hereinafter abbreviated as aluminum phthalocyanine (C)).
The aluminum phthalocyanine represented by the general formula (1) in the crystalline form has a property as a pigment and can be suitably used as a colorant, in particular, a green colorant. Here, (± 0.2) at the diffraction angle 2θ indicates, for example, all values within the range of 6.8−0.2 to 6.8 + 0.2 at 6.8 °.

In Y ₁ in the general formula (1), the alkoxy group having 1 to 5 carbon atoms represented by R ₁ and R ₂ may be linear, branched or cyclic, and is not particularly limited. For example, methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyl An oxy group, a sec-pentyloxy group, a tert-pentyloxy group, a neopentyloxy group etc. are mentioned.

When the alkoxy group represented by R ₁ and R ₂ in Y ₁ in General Formula (1) has 1 to 5 carbon atoms, it becomes easy to obtain various desired properties. Among them, the carbon number of the alkoxy group is preferably 2 to 4 in view of fastness and color characteristics, and a linear alkoxy group is more preferable.

  The following phthalocyanine compounds (a) to (h) may be mentioned as typical examples of the aluminum phthalocyanine represented by the general formula (1) in the present invention, but the present invention is limited thereto is not.

Phthalocyanine compound (a) Phthalocyanine compound (b)


Phthalocyanine compound (c) Phthalocyanine compound (d)


Phthalocyanine compound (e) Phthalocyanine compound (f)


Phthalocyanine compound (g) Phthalocyanine compound (h)

<Method of producing aluminum phthalocyanine>
Then, the manufacturing method of the aluminum phthalocyanine of this invention is demonstrated. The aluminum phthalocyanine represented by the general formula (1) of the present invention is obtained by reacting a hydroxyaluminum phthalocyanine represented by the following chemical formula (2) with a phosphoric acid compound represented by the following general formula (3): The desired aluminum phthalocyanine can be obtained.

(In the general formula (3), each of R ₃ and R ₄ independently represents an alkoxy group having 1 to 5 carbon atoms.
Z represents a chlorine atom, a bromine atom or a hydroxyl group. )

  The reaction of the hydroxyaluminum phthalocyanine represented by the chemical formula (2) with the phosphoric acid compound can be advanced, for example, by mixing and stirring in an organic solvent. Next, the desired organic phthalocyanine can be obtained by removing the organic solvent.

Examples of the organic solvent used in the production of aluminum phthalocyanine include the following.
Monohydric alcohol solvents typified by methanol, ethanol, isopropanol, t-butanol,
Ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivative, glycerin, or trimethylolpropane etc. Polyhydric alcohol solvents represented by
1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N Amide solvents such as N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, urea, tetramethylurea and the like,
In addition, lower monoalkyl ether solvents of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, or triethylene glycol monoethyl (or butyl) ether,
Polyether solvents such as ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), or triethylene glycol dimethyl ether (triglyme)
Sulfur-containing solvents such as sulfolane, dimethylsulfoxide or 3-sulfolene,
Multifunctional solvents such as diacetone alcohol and diethanolamine
Carboxylic acid solvents such as acetic acid, maleic acid, docosahexaenoic acid, trichloroacetic acid, or trifluoroacetic acid,
Sulfonic acid solvents such as methanesulfonic acid or trifluorosulfonic acid,
Aromatic hydrocarbon solvents such as benzene, toluene and xylene.
In one embodiment, monohydric alcohol solvents such as methanol, ethanol, isopropyl alcohol, dimethyl sulfoxide, N, N-dimethylformamide, 1-methyl-2-pyrrolidinone, etc., because the dissolution of the phosphate compound is good. It is preferable to use an aprotic polar solvent such as These organic solvents can be used alone or in combination of two or more.

  As a method of removing the organic solvent after completion of the reaction, any method known in the art can be used. In one embodiment, after suction filtration or pressure filtration, it is desirable to be removed by drying after washing with an organic solvent compatible with the used organic solvent and having a low boiling point. In the case of a water-soluble organic solvent, it is desirable to remove it by washing with water after mixing with water.

  As a method for obtaining the above-mentioned aluminum phthalocyanine (A) (B) (C), for example, the solvent type, reaction time, reaction temperature at the time of reacting hydroxy aluminum phthalocyanine represented by chemical formula (2) with phosphoric acid compound By changing, it is possible to obtain an aluminum phthalocyanine having each X-ray diffraction pattern, but is not limited thereto.

Refinement of aluminum phthalocyanine
As a method of refinement | miniaturization, the industry well-known method used for refinement | miniaturization of general coloring agents and pigments, such as an acid pasting method and solvent salt milling method, is mentioned.

  The acid pasting method is a method of obtaining a fine colorant by adding a pigment in sulfuric acid and dissolving it, and then dropping a sulfuric acid solution into a large amount of water to precipitate it. It is possible to obtain pigment particles having a very fine primary particle diameter and narrow distribution width and sharp particle size distribution by optimizing the amount of water used in precipitation, temperature and the like. it can.

  In the solvent salt milling method, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is heated while using a kneader such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor or sand mill. After mechanical kneading, this is a treatment to remove the water-soluble inorganic salt and the water-soluble organic solvent by washing with water. The water-soluble inorganic salt functions as a crushing aid, and at the time of salt milling, the pigment particles are crushed using the hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate or the like can be used. From the point of price, it is preferable to use sodium chloride (salt). The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, and most preferably 300 to 1000% by mass, based on the total mass (100% by mass) of aluminum phthalocyanine, from both the treatment efficiency and the production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises at the time of salt milling and the solvent is easily evaporated, in view of safety, those having a high boiling point of 120 ° C. or higher are preferable. As such a water-soluble organic solvent, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid Polypropylene glycol or the like is used. These water-soluble organic solvents are preferably used in a range of 5 to 1000% by mass, more preferably 50 to 500% by mass, based on the total mass of aluminum phthalocyanine (100% by mass).

  In the solvent salt milling treatment, a resin may be added as needed. Here, the type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is solid at room temperature, preferably water-insoluble, and more preferably partially soluble in the water-soluble organic solvent. It is preferable that the usage-amount of resin is the range of 2-200 mass% on the basis of the total mass of aluminum phthalocyanine (100 mass%).

  The aluminum phthalocyanine of the present invention may be used in combination of two or more kinds according to the use purpose. In this case, aluminum phthalocyanines produced separately may be used as a mixture. Or you may use what was manufactured by synthesize | combining or refine | miniaturizing two or more types of aluminum phthalocyanines simultaneously.

<Coloring composition>
The coloring composition of the present invention contains a colorant, a binder resin and an organic solvent, and the colorant contains the aluminum phthalocyanine represented by the general formula (1). In one embodiment, the coloring composition has a green color derived from the aluminum phthalocyanine represented by General Formula (1) used as a coloring agent. The coloring composition of the present invention may contain an additional dye as a coloring agent as long as the effect of the aluminum phthalocyanine represented by the general formula (1) is not impaired for the purpose of adjusting the chromaticity and the like.

<Colorant>
(Green pigment)
In one embodiment of the present invention, the coloring composition further contains a green pigment other than the aluminum phthalocyanine represented by the general formula (1) within the range not impairing the effect of the present invention in order to further adjust the chromaticity. It is also good. The green pigment is not particularly limited, but generally includes a green pigment or a green dye.
As a green pigment, for example, C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, JP-A 2008- The zinc phthalocyanine pigments described in JP-A-19383, JP-A-2007-320986, JP-A-2004-70342, the aluminum phthalocyanine pigments described in JP-A-4893859, etc. It is not limited. Among these, from the viewpoint of obtaining high contrast ratio and high brightness, C.I. I. Pigment green 7, 36, 58.

  As a green dye, C.I. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. C.I. I. Solvent dyes, C.I. I. Acid green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. C.I. I. Acid dyes, C.I. I. Direct greens 25, 27, 32, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, and so on. I. Direct dyes, C.I. I. Mordant green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. C.I. I. Mordant dyes and the like can be mentioned. As a green pigment, C.I. I. Pigment Green 7, 36 and 58 is preferably at least one selected from the group consisting of

(Yellow pigment)
The coloring composition of the present invention may contain a yellow dye in order to further adjust the chromaticity, as long as the effects of the present invention are not impaired. The yellow pigment is not particularly limited, but generally includes a yellow pigment or a yellow dye.

  As the yellow pigment, organic or inorganic pigments can be used alone or as a mixture of two or more, and pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferable, Organic pigments are used. As an organic pigment, what is generally marketed can be used, and a natural pigment and an inorganic pigment can be used together according to the hue of the filter segment made desired.

  Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. As yellow pigments, C.I. I. Pigments yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,192,193,194,196,198,199,213,214, may be used yellow pigment quinophthalone pigments described in Japanese Patent No. 4,993,026 discloses. In particular, from the viewpoint of the heat resistance, light resistance and lightness of the filter segment, as a yellow pigment, C.I. I. Pigment Yellow 138, 139, 150 and 185 is preferably at least one selected from the group consisting of

  Examples of yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes And naphthoquinone dyes and oxazine dyes.

  Therefore, as specific examples of yellow dyes, C.I. I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 And the like.

  Also, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 121 126, 127, 129, 132, 133, 134 and the like.

  Also, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like.

  Also, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195 and the like.

  Also, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 , 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

  When a green pigment is used in combination with the aluminum phthalocyanine represented by the general formula (1), the mass ratio of the green pigment / the aluminum phthalocyanine represented by the general formula (1) is 10/90 from the viewpoint of lightness and hue. A range of 70 to 30/30 is preferred. More preferably, it is in the range of 20/80 to 40/60, and still more preferably in the range of 20/80 to 35/65.

  When a yellow pigment is used in combination with the aluminum phthalocyanine represented by the general formula (1), the mass ratio of the yellow pigment / the aluminum phthalocyanine represented by the general formula (1) is 85/15 to 5 in view of lightness and hue. The range of 30/70 is preferred. More preferably, it is in the range of 85/15 to 40/60, and still more preferably in the range of 85/15 to 50/50.

(Finening of coloring agent)
The colorant used in the coloring composition of the present invention is suitable as a colorant for color filters by subjecting colorant particles to refinement, if necessary, by salt milling, etc., in order to obtain high brightness and high contrast. It can be used for The volume average primary particle size of the colorant is preferably 10 nm or more in order to enhance the dispersibility in the colorant carrier. In addition, in order to obtain a filter segment with high contrast, the thickness is preferably 80 nm or less. In one embodiment, it is more preferably in the range of 20 to 60 nm, still more preferably in the range of 30 to 50 nm.

  The salt milling treatment is the same as the solvent salt milling method described above in the section “Fine-izing of aluminum phthalocyanine”.

<Binder resin>
Binder resin should just disperse | distribute coloring agents, such as a pigment and pigment | dye, especially the aluminum phthalocyanine represented by General formula (1). A thermoplastic resin, a thermosetting resin, etc. are mentioned as a specific example of binder resin.

(Thermoplastic resin)
As a thermoplastic resin used for binder resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

(Thermosetting resin)
Examples of the thermosetting resin used for the binder resin include epoxy resin, benzoguanamine resin, rosin modified maleic resin, rosin modified fumaric resin, melamine resin, urea resin, cardo resin, and phenol resin.

  The thermosetting resin may be, for example, low molecular weight compounds such as epoxy compounds, benzoguanamine compounds, rosin modified maleic acid compounds, rosin modified fumaric acid compounds, melamine compounds, urea compounds, cardo compounds, and phenol compounds, and the present invention It is not limited to this. By including such a thermosetting resin, the resin reacts at the time of firing of the filter segment, the crosslink density of the coating film is increased, the heat resistance is improved, and the effect of suppressing pigment aggregation at the time of firing the filter segment is obtained. Be Among these, epoxy resin, cardo resin, or melamine resin is preferable.

When producing a color filter using a coloring composition, the binder resin is a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light range. Is preferred.
The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000, in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  The binder resin is preferably used in an amount of 30 parts by mass or more in resin solid content with respect to 100 parts by mass of the total mass of the colorant, because the film forming property and the various resistances are good. The resin solid content is preferably used in an amount of 500 parts by mass or less, since good color characteristics can be exhibited. In one embodiment, the binder resin is preferably used in an amount of 50 to 500 parts by mass, more preferably 100 to 400 parts by mass, with respect to 100 parts by mass of the total mass of the colorant.

  In one embodiment, when the coloring composition is used in the form of an alkali-developable coloring resist material, an alkali-soluble vinyl resin prepared using an acidic group-containing ethylenic unsaturated monomer from the viewpoint of developability It is preferable to use as a binder resin. In another embodiment, a photosensitive coloring composition may be configured for the purpose of improving photosensitivity and improving solvent resistance. In this case, an active energy ray curable resin having an ethylenically unsaturated double bond can be used as the binder resin. Hereinafter, these embodiments will be described more specifically.

  As a vinyl type alkali soluble resin which can be used suitably as a binder, the homopolymer or copolymer prepared using an ethylenically unsaturated monomer which has acidic groups, such as a carboxyl group, a hydroxyl group, and a sulfone group, for example Can be mentioned. As specific examples of the above-mentioned vinyl alkali-soluble resin, acrylic resin having an acidic group, α-olefin / (maleic anhydride) copolymer, styrene / styrene sulfonic acid copolymer, ethylene / (meth) acrylic acid copolymer Or isobutylene / (anhydride) maleic acid copolymer and the like. Among them, at least one resin selected from (meth) acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers is preferable. In particular, a (meth) acrylic resin having an acidic group is preferably used because of its high heat resistance and transparency.

  As an acidic group in an acidic group containing ethylenically unsaturated monomer used in order to prepare the said resin, what has a carboxylic acid or a hydroxyl group is preferable. Examples of ethylenically unsaturated monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of ethylenically unsaturated monomers having a hydroxyl group include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4 -Hydroxyvinylbenzene, 2-hydroxy-3- phenoxypropyl acrylate, or caprolactone adducts of these monomers (additional mole number is preferably 1 to 5).

  In one embodiment, when forming a photosensitive coloring composition for a color filter, the binder resin comprises a colorant-adsorbing group and an alkali at the time of development from the viewpoints of pigment dispersibility, permeability, developability, and heat resistance. The balance between the carboxyl group acting as a soluble group and the aliphatic and aromatic groups acting as affinity groups for the colorant carrier and solvent is important. In one embodiment, it is preferable to use a resin having an acid value of 20 to 300 mg KOH / g as a binder resin from the viewpoint of pigment dispersibility, permeability, developability, and durability. By using a resin having an acid value within the above range, appropriate solubility in a developer can be obtained, and it becomes easy to form a fine pattern.

  From the above viewpoint, the vinyl-based alkali-soluble resin obtained by polymerizing the above-mentioned acidic group-containing ethylenically unsaturated monomer has an acid value of 20 to 300 mg KOH / g, and a weight average molecular weight (Mw) of 10000 to 80000. Is preferred. In one embodiment, the resin may be a copolymer of methacrylic acid, 2-hydroxyethyl (meth) acrylate, and other monomers such as n-butyl methacrylate.

  As another embodiment, when forming a photosensitive coloring composition as an alkali-developable coloring resist for color filter, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond as a binder resin, In particular, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain. When the above-mentioned resin having an ethylenically unsaturated double bond in the side chain is used as a binder resin, no coating foreign matter is generated after the resist is applied, and the stability of the colorant in the resist material is improved. Tend. When a linear resin having no ethylenically unsaturated double bond in the side chain is used, the colorant is less likely to be trapped by the resin in the liquid in which the resin and the colorant are mixed, and has a degree of freedom. As a result, the colorant component is easily aggregated and precipitated. On the other hand, in the case of using an active energy ray-curable resin having an ethylenically unsaturated double bond in a side chain, the colorant is easily trapped by the resin in a liquid in which the resin and the colorant are mixed. Therefore, in the solvent resistance test, it is difficult for the dye to be eluted and the colorant component is less likely to be aggregated and precipitated. In addition, when forming a film by exposure to active energy rays, the colorant molecules are fixed by three-dimensional crosslinking of the resin, and even if the solvent is removed in the subsequent development step, the colorant components are aggregated and precipitated. It is estimated that it will be difficult to do.

  As an active energy ray curable resin which has the said ethylenically unsaturated double bond, resin which introduce | transduced the unsaturated ethylenic double bond by the method of (a) shown below and (b) is mentioned, for example.

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers And the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is added, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group There is a way to introduce it.

  Examples of unsaturated ethylenic monomers having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate And 3,4-epoxycyclohexyl (meth) acrylates, which may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of the reactivity with the unsaturated monobasic acid in the next step.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxy, halogen, nitro, cyano-substituted, etc. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. It remained by using tricarboxylic acid anhydrides, such as trimellitic acid anhydride, or using tetracarboxylic acid dianhydrides, such as pyromellitic acid dianhydride, as needed, such as increasing the number of carboxyl groups. Anhydride groups can also be hydrolyzed, etc. In addition, when tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as a polybasic acid anhydride, the unsaturated ethylenic double bond can be further increased.

  As a similar method of method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (b)]
As the method (b), by using an unsaturated ethylenic monomer having a hydroxyl group, and copolymerizing with another monomer of an unsaturated monobasic acid having another carboxyl group or another monomer There is a method of reacting the isocyanate group of the unsaturated ethylenic monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  As the unsaturated ethylenic monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (Meth) acrylates or hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate may be mentioned, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and / or butylene oxide etc. to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylates to which (poly) 12-hydroxystearic acid or the like is added can also be used. From the viewpoint of coating foreign matter suppression, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethylisocyanate or 1,1-bis [(meth) acryloyloxy] ethylisocyanate, but are not limited thereto. Alternatively, two or more types can be used in combination.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dissolved in a monomer, a resin and the like, and the filter segment is coated on a substrate such as a glass substrate to a dry film thickness of 0.2 to 5 μm. An organic solvent is included to facilitate formation.

As the organic solvent, for example, ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, There may be mentioned tert-butylbenzene, γ-butyrolactone, isobutyl alcohol and isophorone.
Furthermore, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene Glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol Cole monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol Monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol Cole phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Examples thereof include methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like.
These organic solvents can be used alone or in combination of two or more.

  Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl from the viewpoint of good dispersibility of colorant, permeability and coatability of coloring composition. It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent adjusts the coloring composition to an appropriate viscosity and can form a filter segment having an intended uniform film thickness, so an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the colorant in total. Is preferably used. In one embodiment, the organic solvent is used in an amount of preferably 500 to 2000 parts by mass, more preferably 500 to 1000 parts by mass, with respect to 100 parts by mass of the total mass of the colorant.

<Method of producing coloring composition>
The coloring composition of the present invention preferably contains a coloring agent containing an aluminum phthalocyanine represented by the general formula (1), the binder resin and, if necessary, a solvent, preferably a dye derivative and the like. It can be finely dispersed and manufactured using various dispersing means such as a triple roll mill, a double roll mill, a sand mill, a kneader, or an attritor together with a dispersing aid. In addition, when the solubility of the aluminum phthalocyanine represented by the general formula (1) is high, specifically, the solubility in the organic solvent to be used is high, so long as it is dissolved by stirring and no foreign matter is confirmed, It is not necessary to make it finely dispersed as described above.

  In addition, the coloring composition of the present invention is manufactured by mixing a pigment, an aluminum phthalocyanine represented by the general formula (1), and another colorant separately dispersed in a colorant carrier such as a binder resin. It can also be done.

[Dispersion aid]
When the colorant is dispersed in the colorant carrier, dispersion aids such as dye derivatives, resin type dispersants, surfactants and the like can be used as appropriate. Since the dispersion aid is excellent in the dispersion of the colorant and has a large effect of preventing the reaggregation of the colorant after the dispersion, a coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid is When used, a color filter with high spectral transmittance can be obtained.

  Examples of the dye derivative include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, anthraquinone, acridone or triazine. For example, those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. These can be used, and these can be used individually or in mixture of 2 or more types.

  The compounding amount of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant from the viewpoint of improving the dispersibility. Further, from the viewpoint of heat resistance and light resistance, the above-mentioned compounding amount is preferably 40 parts by mass or less, and most preferably 35 parts by mass or less, with respect to 100 parts by mass of the colorant.

  The resin type dispersant has a pigment affinity site having a property of adsorbing to the colorant, and a site compatible with the colorant carrier, and adsorbs to the colorant to stabilize the dispersion to the colorant carrier It works. Specific examples of the resin type dispersant include polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) with polyester having free carboxyl group, and salts thereof Etc., (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resin, water soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

The following may be mentioned as commercially available resin-type dispersants.
Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 164, 165, 166, 170, 171, 174, 180, 181, by Big Chemie Japan Ltd. 182, 183, 184, 185, 190, 2000, 2001, 2020, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, Or Lactimon, Lactimon-WS or Bykumen etc.
Japan Lubrizol Corporation SOLSPERSE-3000, 9000, 13000, 13240, 13640, 13640, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32500, 32500, 32600, 32600, 32500 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc.
BASF EFKA-46, 47, 48, 452, 4008, 4010, 4015, 4020, 4050, 4050, 4050, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4310 4320, 4330, 4340, 450, 451, 453, 4540, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc.
Addisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine Techno Co., Ltd.

As surfactant, the following is mentioned.
Sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine Anionic surfactants such as lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid ester;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate;
Cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts;
Alkylbetaines such as alkyl dimethylamino acetic acid betaines, and amphoteric surfactants such as alkyl imidazolines.
Although these can be used individually or in mixture of 2 or more types, it is not necessarily limited to these.

When a resin type dispersant and / or a surfactant is added, the amount thereof is preferably 0.1 to 55 parts by mass, more preferably 100 parts by mass of the colorant, from the viewpoint of the effect on dispersion. Is 0.1 to 45 parts by mass.
In one embodiment, the colorant may be separately dispersed prior to the dispersion treatment to the colorant carrier such as the binder resin. That is, after the pigment dispersion is prepared by dispersing the pigment, it may be used as a colorant.

  In one embodiment, the coloring composition of the present invention may further contain at least one of a photopolymerizable monomer and a photopolymerization initiator in the colorant, the binder resin, and the organic solvent. The coloring composition of such an embodiment can be suitably used as a photosensitive coloring composition for color filters. Furthermore, the coloring composition of the present invention may contain, in addition to the components described above, a sensitizer, a multifunctional thiol, an amine compound, a leveling agent, a curing agent, a curing accelerator, and other additive components. . Each component will be described below.

<Photoinitiator>
The coloring composition of the present invention can contain a photopolymerization initiator. It is preferable that it is 5-200 mass parts with respect to 100 mass parts of aluminum phthalocyanines represented by General formula (1), and the compounding quantity at the time of using a photoinitiator is 10-150 from a photocurable viewpoint. More preferably, it is part by mass.

As the photopolymerization initiator, it is possible to use a conventionally known polymerization initiator. Specifically, the following may be mentioned.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl methyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane, oligo [2- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2-hydroxy-1- [4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl] -2 -Acetophenones such as methylpropan-1-one;
Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether;
Phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Other phenylglyoxylic methyl esters etc.
More specifically, Irgacure 651, Irgacure 184, Darocure 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure Cure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01, Irgacure OXE-02 (BASF Corp.), Adeka Optomer N1717, Adeka Optomer N 1919, Adeka Arms NCI- 831 (ADEKA) and Esacure 1001 M (Lamberti).
In addition, triazine derivatives described in JP-B-59-1281, JP-B-61-9621 and JP-A-60-60104, JP-A-59-1504 and JP-A-61-243807. Organic Peroxides, JP-B-43-23684, JP-B-44-6413, JP-B-47-1604, and diazonium compounds described in US Pat. No. 3,567,453, US Pat. No. 2,848,328, US Pat. Organic azide compounds described in Japanese Patent Publication No. 2852379 and U.S. Pat. No. 2,940,853, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015 and Japanese Patent Publication No. 45-9610 Ortho-quinonediazides, JP-B-55-39162, JP-A-59-140203 and "Macromoleculars (MACROM OLECULES)", Volume 10, page 1307 (1977) described various onium compounds including iodonium compounds, JP-A-59-142205 And azo compounds of the following.
Furthermore, Japanese Patent Application Laid-Open Nos. 1-54440, European Patent No. 109851, European Patent No. 126712, and the Journal of Imaging Science (J. IMAG. SCI.), Vol. 30, 174 Metal allene complex described in page (1986), titanocenes described in JP-A-61-151197, "COORDINATION CHEMISTRY REVIEW", vol. 84, pp. 85-277 (1988) And transition metal complexes containing transition metals such as ruthenium described in JP-A-2-182701, aluminate complexes described in JP-A-3-209477, borate compounds described in JP-A-2-157760, and Japanese Patent Application Laid-Open No. 55-127550 and 2,4,5-triarylimidazole dimer described in JP-A-60-202437, carbon tetrabromide, an organic halogen compound described in JP-A-59-107344, sulfonium described in JP-A-5-255347 Complexes or oxosulfonium complexes, JP-A-54-99185, JP-A-63-264560 and amino ketone compounds described in JP-A-10-29977, JP-A-2001-264530, JP-A-2001-261761, JP-A 2000-80068, JP-A 2001-233842, JP-A-2004-534797, JP-A 2006-342166, JP-A 2008-094770, JP-A 2009-40762, JP-A 2010-15025, JP-A 2010-189279, JP-A 2010-189 80, JP-A-2010-526846, JP-A-2010-527338, JP-A-2010-527339, USP 3558309 (1971), USP 4202697 (1980) and JP-A-61-24558. An ester compound etc. are mentioned.

  These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as required. In one embodiment, it is preferable to use an α-aminoalkylphenone-based or oxime ester-based compound from the viewpoint of patterning sensitivity. For example, it is selected from the group consisting of Irgacure 907, Irgacure 369, Irgacure 379, Irgacure OXE-01, Irgacure OXE-02 (manufactured by BASF), and Adeka Optomer N 1919 (manufactured by Adeka) exemplified above. At least one of the following can be used.

<Photopolymerizable monomer>
The photopolymerizable monomer of the present invention includes a monomer or oligomer which is cured by ultraviolet light, heat or the like to form a transparent resin, and these can be used alone or in combination of two or more. More specifically, the photopolymer monomer is a compound having one or more photopolymerizable groups in the molecule, and its molecular weight is typically 1000 or less.

  Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate and epoxy (meth) Acrylate, EO modified bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, di- Various acrylic acid esters such as pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate And methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinyl formamide, acrylonitrile And the like, but the effects of the present invention are not limited to these.

  The photopolymerizable monomer may also contain an acid group. For example, esterified products of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid with dicarboxylic acids; esterified products of polyvalent carboxylic acid and monohydroxyalkyl (meth) acrylates Can be mentioned. Specific examples thereof include monohydroxy oligo acrylates or mono hydroxy oligo methacrylates such as trimethylol propane diacrylate, trimethylol propane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. And free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid Carboxyl group-containing oligoesters of monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, etc. However, the effects of the present invention are not limited to these.

  In one embodiment, from the viewpoint of patterning sensitivity and adhesion to a glass substrate, it is preferable to use a polyfunctional monomer having a plurality of photopolymerizable groups in one molecule. As the polyfunctional monomer, one having 3 to 6 photopolymerizable groups per molecule is desirable. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferably used. For example, trade names "ALONIX M-402" manufactured by Toagosei Co., Ltd. and "A-DPH" manufactured by Shin-Nakamura Chemical Co., Ltd. can be used.

  The content of the photopolymerizable monomer is preferably 10 to 300 parts by mass, more preferably 10 to 200 parts by mass, with respect to 100 parts by mass of the colorant, from the viewpoint of photocurability and developability. More preferably, it is used in an amount of 20 to 100 parts by mass.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer. Examples of sensitizers include benzophenone derivatives, unsaturated ketone derivatives such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, teto Benzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrilium derivative, thiopyrilium derivative, tetraphilin derivative, anurene derivative, spiropyran Examples include derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes and the like, but are not limited thereto.

Further, specific examples include Shin Ogawara et al., "Dye Handbook" (1986, Kodansha), Okawara Shin et al., "Chemicals of functional dyes" (1981 CMC), Tadazori Ikemori et al., Special And dyes and sensitizers described in "Functional materials" (1986, CMC). However, the present invention is not limited to these, and in addition, dyes and sensitizers that absorb light in the ultraviolet to near infrared region may be used. Two or more of these may be used in an arbitrary ratio as needed.
Among the sensitizers exemplified above, as a thioxanthone derivative, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 1-chloro-4 -Propoxy thioxanthone etc. can be mentioned. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-bis (diethylamino) benzophenone and the like. be able to. Examples of coumarins include coumarin 1, coumarin 338, coumarin 102 and the like. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin) and the like. However, it is not limited to these.

  Two or more types of sensitizers may be used at an arbitrary ratio as needed. It is preferable that the compounding quantity at the time of using a sensitizer is 3-60 mass parts with respect to 100 mass parts of total mass of the photoinitiator contained in a coloring photosensitive composition, and a photocurable viewpoint It is more preferable that it is 5-50 mass parts. In one embodiment, it is preferable to use benzophenone derivatives from the viewpoint of patterning sensitivity. For example, the brand name "EAB-F" made by Hodogaya Chemical Industry can be used, for example.

<Multifunctional thiol>
The coloring composition of the present invention can contain a multifunctional thiol which acts as a chain transfer agent. The polyfunctional thiol may be any compound having two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bis thioglycollate, ethylene glycol bis thiopropionate, trimethylol propane tris thio glycolate, trimethylol propane tris thio propionate, trimethylol propane tris (5-mercaptobutyrate), pentaerythritol tetrakis thio glycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapic acid -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine.
These polyfunctional thiols can be used alone or in combination of two or more at any ratio as required.

  The content of the multifunctional thiol is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass, based on the mass (100% by mass) of the total solid content of the coloring composition. When the content of the polyfunctional thiol is less than 0.1% by mass, the addition effect of the multifunctional thiol is insufficient, and when it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

<Amine compounds>
In addition, the coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen. As such an amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethyl paratoluidine etc. are mentioned.

<Leveling agent>
It is preferable to add a leveling agent to the colored composition of the present invention in order to improve the leveling properties of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370, etc. are mentioned. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. It is preferable to use the leveling agent content in a proportion of 0.003 to 0.5% by mass in total 100% by mass of the coloring composition.

  Particularly preferable as the leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. More specifically, it is preferable to have the characteristics of having a low solubility in water while having a hydrophilic group and having a low surface tension reducing ability when added to a coloring composition. In addition, those having good wettability to glass plates despite the low surface tension lowering ability are useful, and furthermore, those capable of sufficiently suppressing the chargeability at an addition amount at which defects in the coating film due to foaming do not appear It can be used preferably. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

  The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.

  Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And polyoxyalkylene alkyl ethers such as polyethylene glycol monolaurate; alkyl betaines such as alkyl dimethylamino acetic acid betaine; amphoteric surfactants such as alkyl imidazoline; and fluorine-based and silicone-based surfactants.

<Hardening agent, hardening accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening agent, the hardening accelerator, etc. as needed. As a curing agent, a phenolic resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound and the like are effective, but not particularly limited thereto, a thermosetting resin Any curing agent may be used as long as it can react with it. Among these, a compound having two or more phenolic hydroxyl groups in one molecule, and an amine curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg, dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg, Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- The -4- methylimidazole etc., phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), s-triazine derivatives (eg 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct etc. can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

<Other additive components>
The coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity over time of the composition. Further, in order to enhance the adhesion to the transparent substrate, an adhesion improver such as a silane coupling agent may be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine, etc. Organic phosphine, phosphite and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the colorant.

  Adhesion improvers include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (5,5, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (5,4-epoxycyclohexyl) methyltrimethoxysilane, β- (5,4-epoxycyclohexyl) ethyltriethoxysilane, β- (5,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyl trie Xysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the total amount of the colorant in the coloring composition.

  Although not particularly limited, in one embodiment, the coloring composition includes a colorant containing an aluminum phthalocyanine represented by General Formula (1), a binder resin, and an organic solvent. Here, as the binder resin, it is preferable to use a vinyl-based alkali-soluble resin prepared using an acidic group-containing ethylenically unsaturated monomer. In another embodiment, the coloring composition further contains a photopolymerization initiator and a photopolymerizable monomer in addition to the above components. In another embodiment, the coloring composition further comprises a sensitizer in addition to the above components. In these embodiments, in particular, a vinyl-based alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer is used as a binder resin, and a plurality of photopolymerizable groups are contained in one molecule as a photopolymerizable monomer. It is preferable to use the polyfunctional monomer which it has. Here, as the binder resin, it is more preferable to use a copolymer of a (meth) acrylic polymerizable monomer having an acidic group and another polymerizable monomer. According to such an embodiment, it becomes easy to obtain a coloring composition excellent in developability, pattern sensitivity, and glass adhesion.

<Removal of coarse particles>
The coloring composition of the present invention can be produced by finely dispersing each component using various dispersing means as described above. In one embodiment, coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, more preferably 0.5 μm or larger, in the coloring composition by means of centrifugation, sintered filter, membrane filter, etc. It is preferred to carry out the removal of particles and entrapped dust. Here, the coarse particles mean a secondary particle state in which primary particles are aggregated. Therefore, the coloring composition preferably contains substantially no secondary particles of 0.5 μm or more. In one embodiment, the particle size of the particles in the coloring composition is preferably less than 0.5 μm, and more preferably 0.3 μm or less.

<Color filter>
The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Also, the color filter may further include a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment.

  Examples of base materials such as transparent substrates constituting color filters include glass plates such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate. Used. In addition, on the surface of a glass plate or a resin plate, a transparent electrode made of indium oxide, tin oxide or the like may be formed for driving liquid crystal after panelization.

<Method of manufacturing color filter>
The color filter of the present invention can be produced by a printing method or a photolithography method using the above-mentioned coloring composition.

  Since formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as printing ink, it is low-cost as a manufacturing method of a color filter, and excellent in mass productivity. There is. Furthermore, with the development of printing technology, printing of fine patterns with high dimensional accuracy and smoothness can be performed. In order to print, it is preferable to set it as a composition which an ink does not dry and solidify on the printing plate or on a blanket. In addition, control of the flowability of the ink on the printing press is also important, and the preparation of the ink viscosity can also be performed by the dispersant and the extender pigment.

  When a filter segment is formed by photolithography, the coloring composition prepared as the above-mentioned solvent development type or alkali development type coloring resist material is coated on a transparent substrate by spray coating, spin coating, slit coating, roll coating, etc. The dry film is applied to a thickness of 0.2 to 5 μm by a method. The film dried if necessary is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, it is immersed in a solvent or an alkaline developer, or the developer is sprayed by a spray or the like to remove an uncured portion to form a desired pattern. A color filter can be manufactured by repeating the same operation as this for other colors. Furthermore, in order to accelerate | stimulate superposition | polymerization of a coloring resist material, heating can also be given as needed. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above-mentioned printing method.

  In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the ultraviolet exposure sensitivity, after applying and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method, etc. in addition to the above method, but the coloring composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. . In the transfer method, filter segments are formed in advance on the surface of a peelable transfer base sheet, and the filter segments are transferred to a desired substrate.

  Before forming the color filter segments on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, although a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, it is not limited thereto. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or the reflective substrate and then the color filter segments may be formed. Moreover, an overcoat film, a transparent conductive film, etc. are formed on the color filter of this invention as needed.

  The color filter is bonded to the opposing substrate using a sealing agent, and liquid crystal is injected from the injection port provided in the seal portion, and then the injection port is sealed, and a polarizing film or retardation film is formed on the outside of the substrate as necessary. By bonding, a liquid crystal display panel is manufactured.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), critical alignment (VA), and optically convensend bend (OCB). Etc. can be used in a liquid crystal display mode in which coloring is performed using a color filter.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively.

The following examples relate to the aluminum phthalocyanine of the present invention. Evaluation of the pigment manufactured in each Example was performed as follows.
<Evaluation of pigment>
(Identification of phthalocyanine)
Identification of phthalocyanine is based on coincidence of the molecular ion peak of mass spectrum obtained using time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics) with the mass number obtained by calculation, and It carried out by agreement with the ratio of carbon, hydrogen, and nitrogen obtained using an elemental analyzer (2400CHN elemental analyzer, Perkin-Elmer company make), and a theoretical value.

(Volume average primary particle size (MV))
The volume average primary particle size (MV) was determined by Hitachi High-Technologies Corporation transmission electron microscope (TEM) “H-7650” and the following formula. First, the colorant particles were photographed by TEM. In the obtained image, 100 arbitrary pigments or colorant particles were selected, and the average value of the minor axis diameter and the major axis diameter of the primary particles was taken as the particle diameter (d) of the colorant particles. The volume (V) of the particles was then determined for each pigment or colorant, respectively, as spheres having the previously determined particle size (d). This work was carried out on 100 pigment or colorant particles, and from this, it was calculated using the following formula (1).

Formula (1)
MV = Σ (V · d) / Σ (V)

  The X-ray diffraction pattern by CuKα ray was measured at an X-ray sampling interval of 0.02 ° in the range of diffraction angle 2θ = 3 ° to 35 ° using a table-top type X-ray diffractometer manufactured by Rigaku Corporation. .

<Production of aluminum phthalocyanine>
Example 1
(Production of aluminum phthalocyanine (P-1))
In a reaction vessel, 1250 parts of n-amyl alcohol, 225 parts of phthalonitrile and 78 parts of anhydrous aluminum chloride were mixed and stirred. To this was added 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water while stirring to obtain a blue slurry. The slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of a chloroaluminum phthalocyanine represented by the following chemical formula (4). The elemental analysis of the obtained chloroaluminum phthalocyanine gave the calculated values (C) 66.85%, (H) 2.80%, and (N) 19.49% to the measured value (C) 66. It was 7%, (H) 3.0%, (N) 19.2% and was identified as the target compound.

  Then, in a reaction vessel, 100 parts of chloroaluminum phthalocyanine was added to 1200 parts of concentrated sulfuric acid at room temperature. After stirring at 40 ° C. for 3 hours, the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The formed blue precipitate was filtered, washed with water and dried to obtain 92 parts of a hydroxyaluminum phthalocyanine represented by the following chemical formula (2). The elemental analysis of the obtained hydroxyaluminum phthalocyanine gave the calculated values (C) 69.06%, (H) 3.08%, and (N) 20.14% to the actual values (C) 69. It was 1%, (H) 3.2%, (N) 20.1%, and was identified as the target compound.

  Next, in a reaction vessel, 1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of the above hydroxyaluminum phthalocyanine and 37 parts of chlorodiethylphosphoric acid were added. After reacting for 3 hours at 25 ° C., the solution was poured into 3000 parts of water. The reaction product was filtered, washed with 6000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 112 parts of aluminum phthalocyanine (P-1). About the obtained aluminum phthalocyanine (P-1), the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it identified as a target compound. The volume average primary particle diameter of the obtained aluminum phthalocyanine (P-1) was 35 nm. In addition, when X-ray diffraction pattern by CuKα ray was measured, as shown in FIG. 1, diffraction angles 2θ = 6.8 °, 11.4 °, 15.7 °, 23.7 °, and 24.7 °. It had a peak.

Example 2
(Production of aluminum phthalocyanine (P-2))
In a reaction vessel, 1200 parts of methanol, 100 parts of hydroxyaluminum phthalocyanine obtained in Example 1, and 37 parts of chlorodiethylphosphoric acid were added and reacted at 50 ° C. for 6 hours. The product was filtered, washed with 1800 parts of methanol and then with 1800 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 115 parts of aluminum phthalocyanine (P-2). About the obtained aluminum phthalocyanine (P-2), the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it identified as a target compound. The volume average primary particle diameter of the obtained aluminum phthalocyanine (P-2) was 40 nm. In addition, when the X-ray diffraction pattern by the CuKα ray was measured, as shown in FIG. 2, it had peaks at diffraction angles 2θ = 6.7 °, 11.3 °, 16.6 °, and 25.5 °. The

[Example 3]
(Production of aluminum phthalocyanine (P-3))
1000 parts of 1-methyl-2- pyrrolidinone, 100 parts of hydroxy aluminum phthalocyanine obtained in Example 1, and 45 parts of dibutyl phosphate were added to a reaction vessel, and reacted at 60 ° C. for 4 hours. Then, 1000 parts of water is added dropwise to this solution over 2 hours, and then the reaction product is filtered, washed with 6000 parts of water, dried overnight at 60 ° C. under reduced pressure, and 121 parts of aluminum phthalocyanine (P- I got 3). About the obtained aluminum phthalocyanine (P-3), the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it identified as a target compound. The volume average primary particle diameter of the obtained aluminum phthalocyanine (P-3) was 38 nm. In addition, when X-ray diffraction pattern by CuKα ray was measured, as shown in FIG. 3, diffraction angles 2θ = 4.6 °, 6.7 °, 9.5 °, 11.3 °, 15.6 °, and It had a peak at 24.0 °.

Example 4
(Production of aluminum phthalocyanine (P-4))
In a reaction vessel, 1200 parts of ethylene glycol, 100 parts of the hydroxyaluminum phthalocyanine obtained in Example 1, and 45 parts of dibutyl phosphate were added and reacted at 120 ° C. for 6 hours. The product was filtered, washed with 1800 parts of methanol and then with 1800 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 124 parts of aluminum phthalocyanine (P-4). About the obtained aluminum phthalocyanine (P-4), the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it identified as a target compound. The volume average primary particle diameter of the obtained aluminum phthalocyanine (P-4) was 45 nm. In addition, when the X-ray diffraction pattern by the CuKα ray was measured, as shown in FIG. 2, it had peaks at diffraction angles 2θ = 6.8 °, 11.4 °, 16.6 °, and 25.6 °. The

[Example 5]
(Production of aluminum phthalocyanine (P-5))
In a reaction vessel, 1500 parts of N, N-dimethylformamide, 100 parts of hydroxyaluminum phthalocyanine obtained in Example 1, and 31 parts of dimethyl chlorophosphonate are added and reacted at 25 ° C. for 3 hours, then in 3000 parts of water The solution was injected into the The reaction product was filtered, washed with 6000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 107 parts of aluminum phthalocyanine (P-5). About the obtained aluminum phthalocyanine (P-5), the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it identified as a target compound. The volume average primary particle diameter of the obtained aluminum phthalocyanine (P-5) was 34 nm. In addition, when the X-ray diffraction pattern by CuKα ray was measured, as shown in FIG. 1, diffraction angles 2θ = 7.0 °, 11.6 °, 16.0 °, 23.9 °, and 25.1 °. It had a peak.

[Example 6]
(Production of aluminum phthalocyanine (P-6))
In a reaction vessel, 1500 parts of dimethyl sulfoxide, 100 parts of hydroxyaluminum phthalocyanine obtained in Example 1, and 39 parts of diisopropyl phosphate are added, reacted at 25 ° C. for 3 hours, and the solution is poured into 3000 parts of water. did. The reaction product was filtered, washed with 6000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 117 parts of aluminum phthalocyanine (P-6). About the obtained aluminum phthalocyanine (P-6), the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it identified as a target compound. The volume average primary particle diameter of the obtained aluminum phthalocyanine (P-6) was 37 nm. In addition, when X-ray diffraction pattern by CuKα ray was measured, as shown in FIG. 1, diffraction angles 2θ = 6.7 °, 11.3 °, 15.8 °, 23.7 °, and 24.9 °. It had a peak.

[Example 7]
(Production of aluminum phthalocyanine (P-7))
In a reaction vessel, 1000 parts of xylene, 100 parts of hydroxyaluminum phthalocyanine obtained in Example 1, and 51 parts of diisoamyl phosphate were added, and reacted at 120 ° C. for 6 hours. The product was filtered, washed with 1800 parts of methanol and then with 1800 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 126 parts of aluminum phthalocyanine (P-7). About the obtained aluminum phthalocyanine (P-7), the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it identified as a target compound. The volume average primary particle diameter of the obtained aluminum phthalocyanine (P-7) was 42 nm. In addition, when X-ray diffraction pattern by CuKα ray was measured, as shown in FIG. 3, diffraction angles 2θ = 4.8 °, 6.8 °, 9.8 °, 11.4 °, 15.6 °, and It had a peak at 24.1 °.

The chemical structures, X-ray diffraction patterns and volume primary particle sizes of the aluminum cyanines produced in Examples 1 to 7 are shown in Table 1.

(Production of Comparative Aluminum Phthalocyanine (P-8))
Comparative Example 1
The hydroxy aluminum phthalocyanine manufactured by the method similar to Example 1 was made into aluminum phthalocyanine (P-8). The volume average primary particle diameter of the obtained aluminum phthalocyanine (P-8) was 30 nm.

(Production of comparative aluminum phthalocyanine (P-9))
Comparative Example 2
In a reaction vessel, 2000 parts of N, N-dimethylformamide, 100 parts of the hydroxyaluminum phthalocyanine obtained in Example 1, and 53.9 parts of diphenyl phosphate were added. After reacting at 85 ° C. for 3 hours, the solution was poured into 12000 parts of water. The reaction product was filtered, washed with 24000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 123 parts of aluminum phthalocyanine (P-9). About the obtained aluminum phthalocyanine (P-9), the peak corresponding to the same molecular weight was confirmed from the mass spectrum, and it identified as a target compound. The volume average primary particle diameter of the obtained aluminum phthalocyanine (P-9) was 32 nm.

<Coloring composition>
The following examples relate to a coloring composition (pigment dispersion) using the aluminum phthalocyanine prepared above. The dispersant and binder resin used were produced as follows.

<Method of producing binder resin>
(Preparation of methacryl resin solution 1)
70.0 parts of cyclohexanone is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirring device are attached to a separable four-necked flask, the temperature is raised to 80 ° C., and the inside of the reaction vessel is purged with nitrogen 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Alonix M110" manufactured by Toagosei Co., Ltd.), A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of a methacrylic resin having a weight average molecular weight (Mw) of 26000.
After the resin solution was cooled to room temperature, about 2 g of the resin solution was sampled, dried by heating at 180 ° C. for 20 minutes, and the nonvolatile matter was measured. Then, in consideration of the measured value, a methacrylic resin solution 1 was prepared by adding propylene glycol monoethyl ether acetate to the resin solution obtained above so that the nonvolatile content was 40% by mass.

<Evaluation of resin>
(Polymerization average molecular weight (Mw) of resin)
It is the weight average molecular weight (Mw) of polystyrene conversion measured by GPC (The Tosoh Corp. make, HLC-8120GPC) equipped with RI detector using TSKgel column (made by Tosoh Corp.), using THF as a developing solvent.

(Acid number of resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1.0 parts of the resin solution, and the mixture is stirred and uniformly dissolved, using a 0.1 mol / L KOH aqueous solution as a titration solution, an automatic titrator ("COM-555") The acid value of the resin solution was measured by titration using Hiranuma Sangyo Co., Ltd.). And the acid value per solid content of resin was computed from the acid value of resin solution, and solid content concentration of resin solution.

<Preparation of Resin Type Dispersant Solution>
A resin-type dispersant solution 1 was obtained by mixing a commercially available resin-type dispersant, EFKA 4300 manufactured by BASF, and propylene glycol monomethyl ether acetate to prepare a solution having a nonvolatile content of 40% by mass.

<Production of pigment dispersion>
[Example 8]
(Pigment dispersion (GP-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads of 0.5 mm in diameter. Thereafter, the obtained mixture was filtered with a filter having a pore diameter of 5.0 μm to prepare a pigment dispersion (GP-1) having a nonvolatile component of 20% by mass.
Aluminum phthalocyanine (P-1): 11.0 parts Methacrylic resin solution 1: 17.5 parts Propylene glycol monomethyl ether acetate (PGMAC): 66.5 parts Resin type dispersant solution 1: 5.0 parts

[Examples 9-14, Comparative Examples 3 and 4]
(Pigment dispersion (GP-2) to (GP-9))
Pigment dispersions (GP-2) to (GP-9) were produced in the same manner as in Example 8 except that the aluminum phthalocyanine (P-1) was changed to the aluminum phthalocyanine shown in Table 2.

<Evaluation of pigment dispersion>
The following evaluation was performed about the pigment dispersions (GP-1)-(GP-9) obtained by the Example and the comparative example. The results are shown in Table 2.

(Contrast ratio (CR) evaluation of coating film)
The light emitted from the liquid crystal display backlight unit is polarized through the polarizing plate, passes through the coating of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, light passes through the polarizing plate if the polarizing planes of the polarizing plate and the polarizing plate are parallel, but light is blocked by the polarizing plate if the polarization planes are orthogonal to each other. However, when light polarized by the polarizing plate passes through the coating film of the coloring composition, the colorant particles cause scattering or the like, and when deviation occurs in part of the polarization plane, transmission occurs when the polarizing plates are parallel. The amount of light to be reduced decreases, and when the polarizing plates are orthogonal, some light is transmitted. The transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plates were parallel to the brightness when the polarizing plates were orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (brightness in parallel) / (brightness in orthogonal)
Therefore, when scattering occurs due to the colorant in the coating, the brightness in parallel decreases and the brightness in orthogonal increases, so the contrast ratio decreases.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as a luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as a polarizing plate. In the measurement, it measured through the black mask which opened the 1-cm square hole in the measurement part.

The pigment dispersions are respectively coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 60 minutes and allowed to cool The coated substrate was produced by The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. The contrast ratio was determined according to the following criteria.
:: over 9000: extremely good ○: over 6000 to less than 9000: good Δ: over 3000 to less than 6000: practicable ×: less than 3000: defective

(Evaluation of heat resistance of coating film)
The pigment dispersions are respectively coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 60 minutes, and allowed to cool The coated substrate was produced by The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. [L * (1), a * (1), b * (1)] was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) of the obtained coating film. Further, the chromaticity [L * (2), a * (2), b * (2)] after heat treatment at 250 ° C. for 60 minutes is measured, and the color difference ΔE * ab is determined by the following equation (1) The
Formula (1)
ΔE * ab = [[L * (2) -L * (1)] ² + [a * (2) -a * (1)] ² + [b * (2) -b * (1)] ² ] ^1/2

The heat resistance was determined according to the following criteria.
:: ΔE * ab = 1 or less: extremely good ○: ΔE * ab = 1 to 3: good Δ: ΔE * ab = 3 to 5: practicable ×: ΔE * ab = 5 or more: defective

(Evaluation of light resistance of coating film)
The pigment dispersions are respectively coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 60 minutes and allowed to cool The coated substrate was produced by The prepared coated substrate was adjusted to have a film thickness of 1.5 μm after heat treatment at 230 ° C. A UV cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya) is attached on the substrate, and the color before and after UV light irradiation for 150 hours is measured using a 470 W / m ² xenon lamp, and the above formula (1) The color difference ΔE * ab was determined by The judgment criteria are the same as at the time of heat resistance evaluation.

  In the coloring composition containing the aluminum phthalocyanine of this invention shown to Examples 8-14, the result which was excellent in high contrast ratio and fastness (heat resistance, light resistance) resulted. On the other hand, as in Comparative Example 3 and Comparative Example 4, when the structure was different from the aluminum phthalocyanine of the present invention, both the contrast ratio and the fastness were low. From this result, it is understood that the aluminum phthalocyanine of the present invention is effective for achieving both the contrast ratio and the fastness.

  The following examples relate to a photosensitive coloring composition using aluminum phthalocyanine and a color filter using the photosensitive coloring composition. In the photosensitive coloring composition, pigments other than aluminum phthalocyanine and their pigment dispersions were prepared as follows.

<Production of other finely divided pigments>
(Production of micronized green pigment (PG 58-1))
Phthalocyanine-based green pigment C.I. I. Pigment Green 58 ("FASTOGEN GREEN A110" manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain a finely divided green pigment (PG 58-1).

(Production of micronized green pigment (PG 7-1))
Phthalocyanine-based green pigment C.I. I. Pigment Green 7 ("GreenGNX" manufactured by CLARIANT), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain a finely divided green pigment (PG 7-1).

(Production of micronized green pigment (PG 36-1))
Phthalocyanine-based green pigment C.I. I. Pigment Green 36 ("Green 8 G" manufactured by CLARIANT), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, sodium chloride and diethylene glycol were removed by repeated washing with water, and then dried overnight at 85 ° C. to obtain a finely divided green pigment (PG 36-1).

(Production of micronized yellow pigment (PY150-1))
Nickel complex yellow pigments C.I. I. Pigment Yellow 150 (Lanexcess "E-4GN"), 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8 liters of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain a finely divided yellow pigment (PY150-1).

(Production of micronized yellow pigment (PY138-1))
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 ("Paliotol Yellow L 0962 HD" manufactured by BASF Corporation), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8 liters of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, sodium chloride and diethylene glycol were removed by repeated washing with water, and then dried overnight at 85 ° C. to obtain a finely divided yellow pigment (PY138-1).

(Production of micronized yellow pigment (PY139-1))
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 ("Paliotol Yellow L 2146 HD" manufactured by BASF Corporation), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8 liters of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain a finely divided yellow pigment (PY139-1).

(Production of micronized yellow pigment (PY185-1))
Isoindoline yellow pigment C.I. I. Pigment Yellow 185 (BASF "Paliotol Yellow L 1155") 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8 liters of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain a finely divided yellow pigment (PY185-1).

(Production of micronized red pigment (PR254-1))
Diketopyrrolopyrrole pigment C.I. I. 200 parts of CI Pigment Red 254 ("B-CF" manufactured by BASF Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80C for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried at 85 ° C. overnight to obtain 190 parts of a finely divided diketopyrrolopyrrole pigment (PR254-1).

(Production of micronized red pigment (PR177-1))
Anthraquinone red pigment C.I. I. Pigment Red 177 ("Chromophthal Red A2B" manufactured by BASF Corporation), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain anthraquinone-based finely divided red pigment (PR177-1).

(Production of micronized blue pigment (PB 15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 ("LIONOL BLUE ES" manufactured by Toyo Color Co., Ltd., specific surface area 60 m ² / g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts in a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) And kneading at 80 ° C. for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain a finely divided blue pigment (PB 15: 6-1).

(Production of micronized purple pigment (PV23-1))
Dioxazine purple pigment C.I. I. Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Color Corp.), 200 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, this kneaded material was introduced into 8000 parts of hot water and stirred for 2 hours while heating to 80 ° C. to form a slurry. The slurry was filtered, and after repeated washing with water to remove sodium chloride and diethylene glycol, the slurry was dried overnight at 85 ° C. to obtain a purple refined purple pigment (PV23-1).

<Production of other finely divided pigment dispersions>
(Production of micronized pigment dispersion (GP-10) to (VP-1))
Pigment dispersions (GP-10) to (VP-1) were produced in the same manner as in Example 8 except that aluminum phthalocyanine (P-1) was changed to the finely divided pigment shown in Table 3.

<Production of Photosensitive Colored Composition>
[Example 15]
(Green photosensitive coloring composition (GR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore size of 1 μm to prepare a green photosensitive coloring composition (GR-1).
Pigment dispersion (GP-1): 12.3 parts PY 150, pigment dispersion (YP-1): 37.7 parts Methacrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "ALONIX" M-402 "): 2.0 parts Photopolymerization initiator (" IRGACURE 907 "manufactured by BASF Corporation): 1.2 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Industry Co., Ltd.): 0.3 parts Cyclohexanone: 39.0 parts

[Examples 16 to 27, Comparative Examples 5 and 6]
Green photosensitive coloring compositions (GR-2) to (GR) were prepared in the same manner as in Example 15, except that the breakdown of 50 parts of the total of the pigment dispersion was changed to the components and parts by mass shown in Table 4, respectively. -15) was obtained.

<Evaluation of photosensitive coloring composition>
The following evaluation was performed about the photosensitive coloring composition obtained by the Example and the comparative example. The results are shown in Table 4.
(Evaluation of lightness)
The photosensitive coloring composition was coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater. The coated film was then dried at 70 ° C. for 20 minutes and then heated at 230 ° C. for 60 minutes. Thus, a coated substrate was obtained such that the chromaticity of the substrate was x = 0.297, y = 0.570 in the C light source. The lightness (Y) of the obtained substrate was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Evaluation criteria are as follows.
:: 63.0 or more: extremely good ○: 61.5 or more and less than 63.0: good :: 60.0 or more and less than 61.5: practicable ×: less than 60.0: defective

(Evaluation of film thickness)
The photosensitive coloring composition was coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater. The coated film was then dried at 70 ° C. for 20 minutes and then heated at 230 ° C. for 60 minutes. Thus, a coated substrate was obtained such that the chromaticity of the substrate was x = 0.297, y = 0.570 in the C light source. The film thickness of the obtained substrate was measured with a surface shape measuring instrument DEKTAK150 (manufactured by ULVAC, Inc.), and the coloring power was evaluated from the value of the film thickness. Evaluation criteria are as follows.
:: less than 1.5 μm: very good ○: 1.5 μm or more and less than 1.7 μm: good Δ: 1.7 μm or more and less than 1.9 μm: practicable x: 1.9 μm or more: defective

(Evaluation of solvent resistance)
The photosensitive coloring composition was applied to a glass substrate on which a black matrix had been previously formed by spin coating, and then dried in a clean oven at 70 ° C. for 20 minutes. Then, the substrate was cooled to room temperature and then exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp. Thereafter, the substrate was spray developed for 30 seconds in a 0.2% by mass aqueous solution of sodium carbonate at 23 ° C., washed with ion exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a stripe-like colored pixel layer on the substrate. The obtained striped green pixels were immersed in N-methyl-2-pyrrolidone (NMP) and methanol (MeOH) for 15 minutes, and the color difference of the green pixel portion before and after the immersion was measured. The color difference measurement method, calculation method, and evaluation criteria were the same as in the evaluation of heat resistance and light resistance.

  As in Examples 15 to 27, the photosensitive coloring composition using the aluminum phthalocyanine of the present invention was excellent in the lightness and coloring power, and at the same time, the solvent resistance was also good. In addition, good results were obtained when the aluminum phthalocyanine of the present invention was used in combination with other green and yellow dyes. On the other hand, in the case of a structure different from the aluminum phthalocyanine of the present invention as in Comparative Example 5 and Comparative Example 6, the results were low in lightness, coloring strength and solvent resistance. From this result, it is understood that the photosensitive coloring composition containing the aluminum phthalocyanine of the present invention is effective as a combination having good lightness, coloring power and solvent resistance.

<Preparation of color filter>
The green photosensitive coloring composition containing the aluminum phthalocyanine of the present invention was used to prepare a color filter. The red and blue photosensitive coloring compositions used were prepared as follows.
(Red photosensitive coloring composition (RR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore size of 1 μm to prepare a red photosensitive coloring composition (RR-1).
PR 254 · pigment dispersion (RP-1): 30.0 parts PR 177 · pigment dispersion (RP-2): 20.0 parts methacrylic resin solution 1: 7.5 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "Alonics M-402": 2.0 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF Corporation): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.): 0. 3 parts cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition (BR-1))
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore diameter of 1 μm to prepare a blue photosensitive colored composition (BR-1).
PB 15: 6 pigment dispersion (BP-1): 45.0 parts PV 23 pigment dispersion (VP-1): 5.0 parts methacrylic resin solution 1: 7.5 parts photopolymerizable monomer (Toago synthesis "Alonics M-402" manufactured by Co., Ltd .: 2.0 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF Corporation): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.): 0.3 parts cyclohexanone: 39.0 parts

[Example 28]
The red photosensitive coloring composition (RR-1) was applied to a glass substrate on which a black matrix is formed in advance by a spin coating method, and then dried in a clean oven at 70 ° C. for 20 minutes. The substrate was then cooled to room temperature, and then exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp.
Thereafter, the substrate was spray developed for 30 seconds in a 0.2% by mass aqueous solution of sodium carbonate at 23 ° C., washed with ion exchanged water, and dried. Further, heat treatment was performed at 230 ° C. for 30 minutes in a clean oven to form a stripe-like colored pixel layer on the substrate.
Next, using the green-sensitive colored composition (GR-1) of the present invention, a green-colored pixel layer was formed in the same manner as the red-colored pixel layer. Furthermore, the blue photosensitive pixel composition was similarly formed using blue photosensitive coloring composition (BR-1), and the color filter (CF-1) was obtained. The formed film thickness of each colored pixel layer was 2.0 μm.

  The brightness and contrast ratio were evaluated for the obtained color filters. The measuring method is the same as in the case of evaluation of the pigment dispersion. The color filters using the green coloring composition of the present invention all had high brightness and excellent results in contrast ratio. From the above, the effect of the aluminum phthalocyanine of the present invention was proved.

Claims (8)

The X-ray diffraction pattern represented by the following general formula (1) and by the CuKα ray has a diffraction angle 2θ (± 0.2) = 6.8 °, 11.4 °, 15.8 °, 23.8 °, It is an aluminum phthalocyanine which has a peak at 24.9 degrees, The coloring agent for color filters characterized by the above-mentioned.

(In the general formula (1), Y ₁ represents —OP (= O) R ₁ R ₂ , wherein R ₁ and R ₂ each independently represent an alkoxy group having 1 to 5 carbon atoms.) The X-ray diffraction pattern represented by the following general formula (1) and by the CuKα ray has peaks at diffraction angles 2θ (± 0.2) = 6.7 °, 11.3 °, 16.6 °, 25.5 ° It is an aluminum phthalocyanine which has a coloring agent for color filters characterized by the above-mentioned.

(In the general formula (1), Y ₁ represents —OP (= O) R ₁ R ₂ , wherein R ₁ and R ₂ each independently represent an alkoxy group having 1 to 5 carbon atoms.) The X-ray diffraction pattern represented by the following general formula (1) and by the CuKα ray has a diffraction angle 2θ (± 0.2) = 4.7 °, 6.8 °, 9.6 °, 9.6 °, 11.4 °, It is an aluminum phthalocyanine which has a peak in 15.6 degrees and 24.0 degrees, The coloring agent for color filters characterized by the above-mentioned.

(In the general formula (1), Y ₁ represents —OP (= O) R ₁ R ₂ , wherein R ₁ and R ₂ each independently represent an alkoxy group having 1 to 5 carbon atoms.)   It is a coloring composition containing a coloring agent, binder resin, and an organic solvent, and the coloring agent contains the coloring agent for color filters as described in any one of Claims 1-3. .   The coloring composition for color filters according to claim 4, wherein the coloring agent further contains at least one of a green pigment and a yellow pigment.   The green pigment is C.I. I. Pigment Green 7, 36 and 58, and at least one selected from the group consisting of C.I. I. The coloring composition for color filters of Claim 5 which is at least 1 sort (s) chosen from the group which consists of pigment yellow 138, 139, 150, and 185.   The coloring composition for color filters according to any one of claims 4 to 6, further comprising at least one of a photopolymerizable monomer and a photopolymerization initiator.   A color filter comprising at least one red filter segment, at least one green filter segment and at least one blue filter segment, wherein the at least one green filter segment is as claimed in any one of claims 4 to 7 A color filter formed by the coloring composition for color filters of