JP5625806B2 - Blue coloring composition for color filter, and color filter - Google Patents

Description

  The present invention relates to a triarylmethane salt-forming compound suitable for forming a blue filter segment (pixel) of a color filter of a color liquid crystal display device, a color composition for color filter formed by blending the triarylmethane salt compound, and a color composition for color filter Is used for a blue filter segment (pixel).

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display by using a twisted nematic (TN) type liquid crystal. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. Along with the advancement, demands for a wide color reproduction area and high reliability are also increasing.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  The color filter production method includes a dyeing method using a dye or a salt-forming dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, and an electrodeposition method. Among these, the dyeing method or the dyeing and dispersing method has a drawback that the heat resistance and light resistance are slightly inferior because the colorant is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as a colorant for the color filter, and a pigment dispersion method is often used as a manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and preparing a photosensitizer and additives in a pigment in which pigment particles as a colorant are dispersed in a transparent resin, and this color resist is applied on a substrate such as a spin coater. It is a method for forming a color filter by forming a coating film with an apparatus, selectively exposing through a mask with an aligner, a stepper, etc., patterning by alkali development and thermosetting, and repeating this operation. .

  Conventionally, as a colorant used for forming a blue filter segment (pixel), in general, a phthalocyanine pigment having excellent resistance and color tone is often used. Phthalocyanine pigments have different crystal types such as α-type, β-type, δ-type, and ε-type, and each has excellent properties such as clearness and high coloring power. It is suitable. As this phthalocyanine pigment, those having various central metals such as copper, zinc, nickel, cobalt, and aluminum are known. Among these, copper phthalocyanine pigments are widely used because they have the clearest color tone. In addition, metal phthalocyanine pigments such as metal-free phthalocyanine pigments, zinc phthalocyanine pigments, aluminum phthalocyanine pigments, and cobalt phthalocyanine pigments have been put into practical use.

  In a display device such as a liquid crystal display device using a conventional cold cathode tube type backlight, a combination of a copper phthalocyanine pigment and a dioxazine pigment is combined with a blue filter segment or a cyan filter segment to achieve high brightness and wide color. The display area could be achieved. However, as described above, the color filter is required to have higher brightness and a wider color reproduction region.

  In order to solve the above problems, a technique has been proposed in which a dye, not a pigment, is dissolved as a colorant in a resin or the like (see, for example, Patent Document 1). It has also been proposed to use a triarylmethane dye, particularly a triarylmethane dye, as a colorant for a color filter used for a blue filter segment (see, for example, Patent Document 2). However, the dye has a problem that it is inferior in heat resistance, light resistance and solvent resistance as compared with the pigment.

  As a method for improving heat resistance, it has also been proposed to use a salt-forming compound of a triarylmethane dye having a naphthalene ring and an aromatic sulfonic acid as a color filter colorant (see, for example, Patent Document 3). Even when a color filter was prepared using this dye, both heat resistance and light resistance were insufficient.

  Furthermore, as a method for improving heat resistance, Patent Document 4 proposes salt formation with phthalocyanine sulfonic acid or anthraquinone sulfonic acid as a counter for triarylmethane dyes. It is generally considered that heat resistance and light resistance can be improved by salt formation with a salt of phthalocyanine sulfonic acid having a large molecular weight and good heat resistance and light resistance. However, even when a color filter is prepared using such a dye, both heat resistance and light resistance are insufficient, and generation of foreign matters on the coating film was also confirmed. Further, salt formation with a pigment such as phthalocyanine sulfonic acid has a problem in that the high brightness inherently possessed by the triarylmethane dye is lowered.

JP-A-6-75375 JP 2001-81348 A JP 2008-304766 A WO2009-107734

  The object of the present invention is excellent in color characteristics, heat resistance, light resistance, solvent resistance, no foreign matter generation on the coating film, stable blue coloring composition for color filters, and color characteristics using the same, The object is to provide a color filter having excellent heat resistance, light resistance and solvent resistance.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a triarylmethane salt-forming compound (A) represented by the following general formula (1) as a colorant for a blue coloring composition for a color filter. And a colorant containing a blue pigment enable high brightness and a wide color reproduction range, and no foreign matter is generated on the coating film. It was made.

  That is, the present invention relates to a blue coloring composition for a color filter comprising at least a coloring agent and a resin, and the coloring agent includes a triarylmethane salt forming compound (A) represented by the following general formula (1) and a blue pigment. The present invention relates to a blue coloring composition for a color filter.

General formula (1)

(Wherein R1A to R1D each independently represent a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a benzyl group which may have a substituent). R1A and R1B, and R1C and R1D may each form a ring.
R2 and R3 each independently represent a hydrogen atom or an alkyl group which may have a substituent.
R4 represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X ⁻ represents ArSO ₃ ^— . Ar represents a naphthalene ring substituted benzene ring substituted with -NH _2, or -NH _2. )

  The present invention also relates to the blue coloring composition for a color filter, wherein the blue pigment is a phthalocyanine pigment.

  In the present invention, the phthalocyanine pigment is C.I. I. It is related with the blue coloring composition for the said color filter characterized by being pigment blue 15: 6.

  The present invention also provides a color filter comprising at least one red filter segment (pixel), at least one green filter segment (pixel), and at least one blue filter segment (pixel), wherein at least one blue filter segment is The present invention relates to a color filter formed from a color filter coloring composition.

In the present invention, it is formed of a blue coloring composition for a color filter using a salt-forming compound of triarylmethane-based basic dye introduced with a phenylindole group and ArSO ₃ ^- and a colorant and a resin containing a blue pigment. By using a color filter, it is possible to obtain a color filter having high brightness and a wide color reproduction region and having excellent resistance by using a salt-forming compound.

  In addition, the transmittance spectrum of the coloring composition for color filters, which is a combination of a conventional copper phthalocyanine blue pigment and a dioxazine pigment, has a peak position in the vicinity of 450 nm, and the transmittance sharply decreases on the short wavelength side of 450 nm or less. ing. On the other hand, the blue coloring composition for a color filter of the present invention contains a triarylmethane salt-forming compound (A) comprising a triarylmethane basic dye and an aromatic sulfonate compound as a colorant, Even on the short wavelength side of 450 nm or less, a high transmittance is maintained as compared with the copper phthalocyanine blue pigment. Therefore, it effectively acts on a peak in the vicinity of 425 to 500 nm of many backlights such as cold cathode fluorescent lamps, and high brightness can be obtained.

  Hereinafter, the present invention will be described in detail.

  The blue coloring composition for a color filter of the present invention includes a colorant carrier containing a resin, a triarylmethane salt-forming compound (A) represented by the following general formula (1) as a coloring agent, and a blue pigment for a color filter It is a coloring composition.

（式中、Ｒ１Ａ〜Ｒ１Ｄは、それぞれ独立に水素原子、置換基を有してもよいアルキル基、置換基を有してもよいフェニル基、または置換基を有してもよいベンジル基を表す。また、Ｒ１ＡとＲ１Ｂ、および、Ｒ１ＣとＲ１Ｄはそれぞれ環を形成しても良い。
Ｒ２とＲ３は、それぞれ独立に水素原子、置換基を有してもよいアルキル基を表す。
Ｒ４は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいフェニル基を表す。
Ｘ^-は、ＡｒＳＯ₃ ^-を表す。Ａｒは、−ＮＨ ₂ で置換されたベンゼン環、または−ＮＨ ₂ で置換されたナフタレン環を表す。） General formula (1)

(Wherein R1A to R1D each independently represent a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a benzyl group which may have a substituent). R1A and R1B, and R1C and R1D may each form a ring.
R2 and R3 each independently represent a hydrogen atom or an alkyl group which may have a substituent.
R4 represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X ⁻ represents ArSO ₃ ^— . Ar represents a naphthalene ring substituted benzene ring substituted with -NH _2, or -NH _2. )

<Colorant>
As a coloring agent of the blue coloring composition for color filters of this invention, the triarylmethane salt-formation compound (A) and blue pigment which can be represented by the said General formula (1) are included.
By combining and mixing the triarylmethane salt forming compound (A) represented by the general formula (1) and the blue pigment, in the vicinity of 425 to 500 nm having the characteristic peaks of many backlights as described above. Thus, the spectral spectrum can have a high transmittance, and higher brightness and wider color reproducibility can be obtained than a conventional color filter combining a copper phthalocyanine pigment and a dioxazine pigment. Furthermore, high heat resistance, light resistance, and solvent resistance can be obtained by salting a triarylmethane basic dye.

  The triarylmethane salt-forming compound (A) of the present invention is represented by the following general formula (1).

General formula (1)

  In the formula, R1A to R1D each independently represent a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or a benzyl group that may have a substituent. R1A and R1B, and R1C and R1D may each form a ring.

When adjacent R1A and R1B and R1C and R1D form a ring, these may be a ring bridged with a heteroatom. Specific examples of this ring include the following.

  R2 and R3 each independently represent a hydrogen atom or an alkyl group which may have a substituent.

  R4 represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.

  Here, as the alkyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, Isopentyl group, sec-butyl group, t-butyl group, sec-pentyl group, t-pentyl group, t-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, Examples include a boronyl group and a 4-decylcyclohexyl group.

  Examples of the substituent that the alkyl group which may have a substituent, the phenyl group which may have a substituent, and the benzyl group which may have a substituent include a fluorine atom, chlorine Atom, amino group, alkyl group having 1 to 8 carbon atoms, alkenyl group having 1 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy group An alkyl carboxyl group having 2 to 9 carbon atoms, a sulfonic acid amide group, a sulfone alkylamide group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, a carbon number Dialkylaminoethyl group formed by bonding 1-4 alkyl groups, trifluoromethyl group, trialkylsilyl group having 1-8 carbon atoms, nitro group, 1-8 carbon atoms Alkylthio group, a vinyl group, and the like.

  R1A to R1D are preferably an alkyl group having 1 to 8 carbon atoms from the viewpoint of ease of synthesis and color characteristics.

  R2 and R3 are preferably each independently a hydrogen atom or a methyl group from the viewpoint of ease of synthesis and color characteristics.

  R4 is preferably an alkyl group having 1 to 8 carbon atoms or a phenyl group from the viewpoint of ease of synthesis and color characteristics.

X ⁻ represents ArSO ₃ ^— . Ar is to display the naphthalene ring substituted substituted benzene ring or -NH _2, with -NH _2.

  The position of the cation of the triarylmethane dye may be anywhere as long as a stable resonance structure can be obtained, and may be any nitrogen portion of the amine portion or the central carbon portion of the triarylmethane.

For example, the triarylmethane salt-forming compound (A) represented by the general formula (1) was synthesized by refluxing the corresponding benzophenone and the corresponding phenylindole in toluene in the presence of POCl ₃ and substituted with —NH ₂ . can be obtained by the by 1-naphthalene sodium sulfonate and salt exchange substituted benzene sulfonic acid sodium or -NH _2.

General formula (1)

Reference reaction formula

  The use ratio of the blue pigment and the triarylmethane salt forming compound (A) is preferably 1 to 80 parts by weight of the triarylmethane salt forming compound (A) with respect to 100 parts by weight of the blue pigment. More preferably, it is 5 to 60 parts by weight. If the addition amount of the triarylmethane salt-forming compound (A) is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and if it exceeds 80 parts by weight, the hue changes, which is not preferable.

(Blue pigment)
As the blue pigment, a phthalocyanine pigment and / or a triarylmethane lake pigment or the like is used. As the phthalocyanine pigment, it is preferable to use a copper phthalocyanine blue pigment. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The following “CI” means a color index (CI).

  Examples of the copper phthalocyanine blue pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and the like. Among them, copper phthalocyanine blue pigments having ε-type and α-type structures are preferable. Such preferred pigments are specifically C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Blue 15: 1.

Examples of triarylmethane lake pigments include C.I. I. Pigment blue 1, 1: 2, 1: 3, C.I. I. Pigment Blue 2, 2: 1, 2: 2, C.I. I. Pigment blue 3, C.I. I. Pigment Blue 8, C.I. I. Pigment blue 9, C.I. I. Pigment Blue 10, 10: 1, C.I. I. Pigment blue 11, C.I. I. Pigment blue 12, C.I. I. Pigment blue 18, C.I. I. Pigment blue 19, C.I. I. Pigment blue 24, 24: 1, C.I. I. Pigment blue 53, C.I. I. Pigment blue 56, 56: 1, C.I. I. Pigment blue 57, C.I. I. Pigment blue 58, C.I. I. Pigment blue 59, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62 and the like.
Among these, C.I. I. It is preferable to use CI Pigment Blue 15: 6.

(Miniaturization of pigment)
The blue pigment used in the blue coloring composition of the present invention and the optional pigment can be refined by a salt milling treatment. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight based on the total weight of the pigment (100% by weight) from the viewpoint of both processing efficiency and 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 dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. 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 and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment (100% by weight).

(Other colorants)
In addition, other organic pigments can be added to the blue coloring composition of the present invention as long as the effect is not hindered.

In the case of an organic pigment, it is preferable to use a dioxazine pigment, an anthraquinone pigment, an azo pigment, or a quinacridone pigment in combination. Among these, it is preferable to use a dioxazine pigment in combination. Examples of the dioxazine pigment include C.I. I. Pigment Violet 23 is preferably used. By using a dioxazine pigment in combination with the blue coloring composition of the present invention, it is possible to obtain a stable and high-quality blue coloring composition which is further excellent in heat resistance, light resistance and solvent resistance.
In addition, as described above, it is preferable to use an organic pigment that can be used in combination with these by refining it by a method such as salt milling.

(resin)
The resin is one that disperses a colorant, particularly a triarylmethane salt-forming compound (A), or a dye that stains and permeates the triarylmethane salt-forming compound (A), such as a thermoplastic resin or a thermosetting resin. Is mentioned.

  The resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali developing resist for a color filter, coating foreign matter after the triarylmethane salt-forming compound (A) is applied It does not occur, and the stability of the triarylmethane salt-forming compound (A) in the resist material is preferably improved. When a linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the dye is not easily trapped in the resin and dye mixture, and the dye has a degree of freedom. The components tend to aggregate and precipitate, but by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the dye is easily trapped in the resin and dye mixture, Dye components are less likely to agglomerate and precipitate, and even when exposed to active energy rays to form a film, the resin is three-dimensionally cross-linked to fix the dye molecules, and the solvent can be removed in the subsequent development process. It is estimated that the dye component is less likely to aggregate and precipitate.

  The weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, 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.

  When the resin is used as a photosensitive coloring composition for a color filter, from the viewpoint of dispersibility, permeability, developability, and heat resistance of the pigment and the triarylmethane salt forming compound (A), The balance of the carboxyl group that acts as an alkali-soluble group during development, the aliphatic group that acts as an affinity group for the colorant carrier and the solvent, and the aromatic group, the dispersibility, permeability, development of pigments and triarylmethane salt forming compounds The resin having an acid value of 20 to 300 mgKOH / g is preferable. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  Since the resin has good film formability and various resistances, the resin is preferably used in an amount of 30% by weight or more based on the total weight of the colorant (100% by weight), and has a high colorant concentration and good color. Since the characteristics can be expressed, it is preferably used in an amount of 500 wt% or less.

(Thermoplastic resin)
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

(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 is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 2-glycidoxyethyl (meth).
An acrylate, 3,4 epoxy butyl (meth) acrylate, and 3,4 epoxy cyclohexyl (meth) acrylate are mentioned, These may be used independently or may use 2 or more types together. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)
Acrylate is preferred.

As unsaturated monobasic acids, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro,
Examples thereof include monocarboxylic acids such as cyano-substituted products, and these may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.
More than one type may be used together. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the 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 a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

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

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate may be mentioned. The above may be used together. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

(Thermosetting resin)
Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

(solvent)
In the blue coloring composition of the present invention, a colorant is sufficiently dispersed and permeated in a colorant carrier, and applied to a glass substrate or the like so as to have a dry film thickness of 0.2 to 5 μm. In order to facilitate the formation of a solvent, a solvent can be included.
Examples of the solvent include 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-propylacetate , O-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, 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 Methyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol 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 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, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, Acetate Amyl, isobutyl acetate, propyl acetate, and a dibasic acid ester and the like.

  Among them, since the dispersion and dissolution of the pigment of the present invention and the triarylmethane salt forming compound (A) are good, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol It is preferable to use glycol acetates such as monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone.

  A solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, it is 800 to 4000% by weight based on the total weight of the colorant (100% by weight). It is preferable to use it in the quantity.

(dispersion)
The blue coloring composition of the present invention preferably contains a coloring agent containing a blue pigment and a triarylmethane salt-forming compound (A) in a coloring agent carrier comprising the resin and, if necessary, a solvent, preferably a pigment derivative or the like. In addition to the above dispersion aid, it can be produced by finely dispersing using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. The blue colored composition of the present invention can also be produced by mixing blue pigments, triarylmethane salt forming compound (A), other colorants and the like separately dispersed in a colorant carrier.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the pigment carrier using the dispersion aid is used. If so, a color filter with high spectral transmittance can be obtained.

  In the present invention, the triarylmethane salt-forming compound (A) is a preferable combination that can also serve as a dispersion aid for the blue pigment.

  Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.

  In the present invention, a pigment derivative is particularly preferable, and the structure thereof is a compound represented by the following general formula (2).

General formula (2)

P-Ln

(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group n: an integer of 1 to 4 is there)

  Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

  Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. What is currently used can be used, These can be used individually or in mixture of 2 or more types.

  The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, most preferably 3% by weight or more based on the total amount of the colorant (100% by weight) from the viewpoint of improving dispersibility. It is. From the viewpoint of heat resistance and light resistance, the total amount of the colorant is preferably 40% by weight or less, and most preferably 35% by weight or less, based on the total amount (100% by weight).

  The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the total amount of the colorant is based on (100% by weight), preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight. . When the blending amount of the resin type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is affected by an excessive dispersant. May affect.

  The blue coloring composition of the present invention can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

(Photopolymerizable monomer)
The photopolymerizable monomer of the present invention includes a monomer or oligomer that forms a transparent resin by being cured by ultraviolet rays or heat, and these can be used alone or in admixture of two or more. The amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

(Photopolymerization initiator)
In the blue coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator or the like is added to add a solvent developing type or an alkali developing type. It can be adjusted in the form of a colored resist material. The blending amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total amount of the colorant, and 10 to 150% by weight from the viewpoint of photocurability and developability. More preferred.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or ben Benzoin compounds such as rudimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -S-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( 4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4 Triazine compounds such as' -methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O Oxime ester compounds such as (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds Or a titanocene compound or the like is used.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 5 to 200% by weight, based on the total amount of the colorant in the blue coloring composition for color filters (100% by weight), from the viewpoint of photocurability and developability. More preferably, it is 10 to 150% by weight.

(Sensitizer)
Furthermore, the blue coloring composition for a color filter of the present invention can contain a sensitizer.

  Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the colored composition (100% by weight). From the viewpoint of developability, it is more preferably 5 to 50% by weight.

(Amine compounds)
Moreover, the coloring composition for color filters of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  As a particularly preferred leveling agent, it is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, has a hydrophilic group but has low solubility in water, and when added to a blue coloring composition, It has the feature that its surface tension lowering ability is low, and it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and the added amount that does not cause coating film defects due to foaming In this case, those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene 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 stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

(Curing agent, curing accelerator)
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. 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- D Ru-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 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.

<Other additive components>
The blue colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include 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% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the coloring composition (100% by weight).

(Removal of coarse particles)
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. Thus, it is preferable that a blue coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

(Color filter)
Next, the color filter of the present invention will be described. 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, and the at least one blue filter segment is a blue coloring composition for the color filter of the present invention. It is formed using.

  The red filter segment can be formed using a normal red coloring composition comprising a red pigment and a colorant carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, Red pigments such as 281, 282, 283, 284, 285, 286, or 287 are used. Further, a basic dye or a salt-forming compound of an acid dye exhibiting a red color can also be used.

  The red coloring composition includes C.I. I. Pigment orange 43, 71, 73 or the like and / or C.I. I. Pigment 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, 119, 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, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. In addition, a salt forming compound of a basic dye or an acid dye that exhibits orange and / or yellow can be used.

The green filter segment can be formed using a conventional green coloring composition comprising a green pigment and a colorant carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used.
A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment 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, 119, 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, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

(Color filter manufacturing method)
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, 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 UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an IJ method or the like in addition to the above method, but the color filter coloring composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate. The IJ method is a method of manufacturing a color filter by patterning a color filter coloring composition by an ink jet method.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” means “parts by weight”. Moreover, the weight average molecular weight (Mw) of the acrylic resin was measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw) in terms of polystyrene.

  First, acrylic resin solutions, refined pigments, triarylmethane salt forming compounds (A), triarylmethane salt compounds, pigment dispersions, triarylmethane salt forming compound-containing resin solutions, triaryls used in Examples and Comparative Examples It demonstrates from the manufacturing method of a methane type compound containing resin solution, a red resist material, and a green resist material.

<Acrylic resin solution manufacturing method>
(Preparation of acrylic resin solution)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was 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 (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Addition to prepare an acrylic resin solution.

<Production method of fine pigment>
(Preparation of blue fine pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Manufacturing Co., Ltd., specific surface area 60 m 2 / g), 200 parts of sodium chloride, 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) It knead | mixed at 80 degreeC for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue fine pigment 1 were obtained. The BET specific surface area of the blue fine pigment 1 was 80 m ² / g.

(Preparation of blue fine pigment 2)
Triphenylmethane blue pigment C.I. I. 200 parts of Pigment Blue 1 (“Fanal Blue D 6340” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue fine pigment 2 were obtained. The blue fine pigment 2 had a BET specific surface area of 65 m ² / g.

(Preparation of purple fine pigment 1)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of purple fine pigment 1 were obtained. The purple fine pigment 1 had a BET specific surface area of 95 m ² / g.

(Preparation of red fine pigment 1)
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment 1 were obtained. The red fine pigment 1 had a BET specific surface area of 70 m ² / g.

(Preparation of yellow fine pigment 1)
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 ("Irgafore Yellow 2R-CF" manufactured by Ciba Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 120 ° C for 8 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow fine pigment 1 were obtained. The BET specific surface area of the yellow fine pigment 1 was 70 m ² / g.

(Preparation of green fine pigment 1)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of green fine pigment 1 were obtained. The green fine pigment 1 had a BET specific surface area of 75 m ² / g.

(Preparation of yellow fine pigment 2)
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product is put into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of yellow fine pigment 2 were obtained. The BET specific surface area of the yellow fine pigment 2 was 65 m ² / g.

<Method for Producing Triarylmethane Salt Formation Compound (A)>
Triarylmethane salt-forming compound (A-1)

(Synthesis of Compound 1)
4,4′-bis (dimethylamino) benzophenone 4.1 parts (Tokyo Chemicals) and 1-methyl-2-phenylindole (Tokyo Chemicals) 3.2 parts were dissolved in 30 parts of toluene to obtain phosphorus oxychloride 3 .6 parts was added and refluxed for 6 hours. Then, it returned to room temperature, 1N hydrochloric acid was added, and chloroform extracted. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (chloroform / methanol = 4/1). After drying under reduced pressure at 60 ° C., 5.0 parts of Compound 1 was obtained. The yield was 65.5%.

  Compound 1 (1.0 part), sodium 2-amino-1-naphthalenesulfonate (Tokyo Chemicals) (1.0 part), dichloromethane (100 parts) and water (100 parts) were mixed and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 1.3 parts of triarylmethane salt forming compounds (A-1). The yield was 92.0%.

  Triarylmethane salt-forming compound (A-2)

(Synthesis of Compound 2)
Dissolve 5.0 parts of 4,4'-bis (diethylamino) benzophenone (Tokyo Chemicals) and 3.2 parts of 1-methyl-2-phenylindole (Tokyo Chemicals) in 30 parts of toluene, and add phosphorus oxychloride. 6 parts were added and refluxed for 6 hours. Then, it returned to room temperature, 1N hydrochloric acid was added, and chloroform extracted. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (chloroform / methanol = 4/1). After drying under reduced pressure at 60 ° C., 6.1 parts of Compound 2 was obtained. The yield was 71.8%.

  Compound 2 (1.0 part), sodium 2-amino-1-naphthalenesulfonate (Tokyo Chemicals) 0.89 part, dichloromethane (100 parts) and water (100 parts) were mixed and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 1.2 parts of triarylmethane salt formation compounds (A-2). The yield was 89.6%.

  Triarylmethane salt-forming compound (A-3)

(Synthesis of Compound 3)
5.0 parts of 4,4'-bis (diethylamino) benzophenone (Tokyo Chemicals) and 3.0 parts of 2-phenylindole (Tokyo Chemicals) are dissolved in 30 parts of toluene, and 3.6 parts of phosphorus oxychloride is added. And refluxed for 6 hours. Then, it returned to room temperature, 1N hydrochloric acid was added, and chloroform extracted. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (chloroform / methanol = 4/1). After drying under reduced pressure at 60 ° C., 5.7 parts of compound 3 was obtained. The yield was 69.0%.

  Compound 3 (1.0 part), sodium 2-amino-1-naphthalenesulfonate (Tokyo Chemicals) (0.91 part), dichloromethane (100 parts) and water (100 parts) were mixed and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 1.2 parts of triarylmethane salt formation compounds (A-3). The yield was 91.7%.

  Triarylmethane salt-forming compound (A-4)

(Synthesis of Compound 4)
4. 5.0 parts of 4,4′-bis (diethylamino) benzophenone (Tokyo Chemicals) and 3.4 parts of 1-ethyl-2-phenylindole (Tokyo Chemicals) are dissolved in 30 parts of toluene, and phosphorus oxychloride 3. 6 parts were added and refluxed for 6 hours. Then, it returned to room temperature, 1N hydrochloric acid was added, and chloroform extracted. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (chloroform / methanol = 4/1). After drying under reduced pressure at 60 ° C., 6.3 parts of Compound 4 was obtained. The yield was 73.3%.

  Compound 4 (1.0 part), sodium 2-amino-1-naphthalenesulfonate (Tokyo Chemicals) 0.87 part, dichloromethane (100 parts) and water (100 parts) were mixed and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 1.2 parts of triarylmethane salt formation compounds (A-4). The yield was 93.1%.

  Triarylmethane salt-forming compound (A-5)

(Synthesis of Compound 5)
4.1 parts of 1-phenyl-2-phenylindole synthesized with 5.0 parts of 4,4′-bis (diethylamino) benzophenone (Tokyo Chemicals) was dissolved in 30 parts of toluene, and 3.6 parts of phosphorus oxychloride was dissolved. Add and reflux for 6 hours. Then, it returned to room temperature, 1N hydrochloric acid was added, and chloroform extracted. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (chloroform / methanol = 4/1). After drying under reduced pressure at 60 ° C., 7.5 parts of Compound 5 was obtained. The yield was 79.6%.

  Compound 5 (1.0 part), sodium 2-amino-1-naphthalenesulfonate (Tokyo Chemicals) 0.80 part, dichloromethane (100 parts) and water (100 parts) were mixed and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 1.2 parts of triarylmethane salt formation compounds (A-5). The yield was 90.8%.

  Triarylmethane salt-forming compound (A-6)

(Synthesis of Compound 6)
3.8 parts of 1-tert-butyl-2-phenylindole synthesized with 5.0 parts of 4,4′-bis (diethylamino) benzophenone (Tokyo Chemicals) was dissolved in 30 parts of toluene, and 3.6% of phosphorus oxychloride was added. Part was added and refluxed for 6 hours. Then, it returned to room temperature, 1N hydrochloric acid was added, and chloroform extracted. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (chloroform / methanol = 4/1). After drying under reduced pressure at 60 ° C., 7.1 parts of compound 6 was obtained. The yield was 77.9%.

  Compound 6 (1.0 part), sodium 2-amino-1-naphthalenesulfonate (Tokyo Chemicals) 0.83 part, dichloromethane (100 parts) and water (100 parts) were mixed and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 1.2 parts of triarylmethane salt formation compounds (A-6). The yield was 94.3%.

  Triarylmethane salt-forming compound (A-7)

(Synthesis of Compound 7)
To a mixture of 12.5 parts of 4-diethylaminobenzoic acid (Tokyo Chemicals) and 45 parts of toluene, 11.5 parts of thionyl chloride was added and stirred at 80 ° C. for 1 hour, followed by concentration under reduced pressure to obtain acid chloride. In a separate container, 10.2 parts of anhydrous aluminum chloride and 65 parts of 1,2-dichloroethane were added. After cooling in an ice bath, a solution having acid chloride dissolved in 30 parts of 1,2-dichloroethane was added dropwise. After dropping, the mixture was stirred for 15 minutes, 10.0 parts of N, N-diethyl-m-toluidine (Tokyo Chemicals) was added dropwise, returned to room temperature, and stirred for 2 hours. Thereafter, the mixture was poured into ice water, adjusted to pH 11 or higher with 4N sodium hydroxide, and extracted with chloroform. This was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (hexane / ethyl acetate = 4/1). The purified product was further dissolved in THF and reprecipitated with hexane. After drying under reduced pressure at 60 ° C., 7.7 parts of Compound 7 was obtained. The yield was 35.2%.

(Synthesis of Compound 8)
5.2 parts of Compound 7 and 3.2 parts of 1-methyl-2-phenylindole (Tokyo Chemicals) were dissolved in 30 parts of toluene, 3.6 parts of phosphorus oxychloride was added, and the mixture was refluxed for 6 hours. Then, it returned to room temperature, 1N hydrochloric acid was added, and chloroform extracted. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (chloroform / methanol = 4/1). After drying under reduced pressure at 60 ° C., 6.0 parts of compound 8 was obtained. The yield was 69.0%.

  Compound 8 (1.0 part), sodium 2-amino-1-naphthalenesulfonate (Tokyo Chemicals) 0.87 part, dichloromethane (100 parts) and water (100 parts) were mixed and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 1.2 parts of triarylmethane salt formation compounds (A-7). The yield was 92.6%.

  Triarylmethane salt-forming compound (A-8)

(Synthesis of Compound 9)
1.8 parts of paraformaldehyde was dissolved in 13 parts of formic acid at 80 ° C., 20.0 parts of N, N-diethyl-m-toluidine (Tokyo Chemicals) was added, and the mixture was stirred at 90 ° C. for 3 hours. After adding 100 ml of chloroform and washing with water, the chloroform layer was extracted, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Thereafter, unreacted N, N-diethyl-m-toluidine was removed by distillation under reduced pressure to obtain 8.0 parts of Compound 9. The yield was 38.2%.

(Synthesis of Compound 10)
Compound 10 was synthesized by the method described in JP-A-H08-12630 using 8.2 parts of Compound 9. 6.5 parts of Compound 10 was obtained with a yield of 50.7%.

(Synthesis of Compound 11)
5.4 parts of compound 10 and 3.2 parts of 1-methyl-2-phenylindole (Tokyo Chemicals) were dissolved in 30 parts of toluene, 3.6 parts of phosphorus oxychloride was added, and the mixture was refluxed for 6 hours. Then, it returned to room temperature, 1N hydrochloric acid was added, and chloroform extracted. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (chloroform / methanol = 4/1). After drying under reduced pressure at 60 ° C., 5.4 parts of Compound 11 was obtained. The yield was 60.8%.

  Compound 11 (1.0 part), sodium 2-amino-1-naphthalenesulfonate (Tokyo Chemicals) (0.85 part), dichloromethane (100 parts) and water (100 parts) were mixed and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 1.2 parts of triarylmethane salt formation compounds (A-8). The yield was 90.5%.

  Triarylmethane salt-forming compound (A-10)

  Compound 2 1.0 part is dissolved in 100 parts of dichloromethane, and a solution prepared by mixing 0.63 part of 2-aminobenzenesulfonic acid (Tokyo Chemicals) and 0.15 part of sodium hydroxide in 100 parts of water is added thereto. And stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 1.2 parts of triarylmethane salt formation compounds (A-10). The yield was 93.2%.

<Method for producing triarylmethane-based compound>
Triarylmethane compounds (C-1)

  Compound 2 which is an intermediate during the production of the triarylmethane salt-forming compound (A-2) was used.

Triarylmethane compounds (C-2)

  1.0 part of Compound 2, which is an intermediate of the triarylmethane salt-forming compound (A-2), is dissolved in 100 parts of dichloromethane, and 1.2 parts of phthalocyanine sulfonic acid and 0.1 part of sodium hydroxide are added to water. The solution mixed in 100 parts was added and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 2.0 parts triarylmethane type compound (C-2). The yield was 93.0%.

  Triarylmethane compounds (C-3)

  C. I. 1.0 part of Basic Blue 7 (Tokyo Chemicals), 0.95 part of sodium 2-amino-1-naphthalenesulfonate (Tokyo Chemicals), 100 parts of dichloromethane and 100 parts of water were mixed and stirred at room temperature for 2 hours. . Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 1.2 parts of triarylmethane type compounds (C-3). The yield was 90.1%.

<Method for producing pigment dispersion>
(Preparation of pigment dispersion (DP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (DP-1) was produced.

Blue fine pigment 1 (CI Pigment Blue 15: 6): 11.0 parts acrylic resin solution: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts resin type dispersant (Ciba Japan) "EFKA4300"): 1.0 part

  Hereinafter, pigment dispersions (DP-2 to 7) were produced in the same manner as the pigment dispersion (DP-1) except that the pigments were changed to the pigments shown in Table 1.

<Method for Producing Triarylmethane Salt-Forming Compound-Containing Resin Solution and Triarylmethane-Based Compound-Containing Resin Solution>
(Preparation of Triarylmethane Salt-Forming Compound-Containing Resin Solution (DA-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a triarylmethane salt-forming compound-containing resin solution (DA-1).

Triarylmethane salt-forming compound (A-1): 11.0 parts acrylic resin solution: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

Hereinafter, the triarylmethane salt-forming compound-containing resin solution described above except that the triarylmethane salt-forming compound (A-1) is changed to the triarylmethane salt-forming compound (A) or the triarylmethane-based compound shown in Table 2 In the same manner as (DA-1), triarylmethane salt-forming compound-containing resin solutions (DA-2 to 8 ) and triarylmethane-based compound-containing resin solutions (DC-1 to 3) were prepared.

<Method for producing red and green resist materials>
(Preparation of red resist material)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a red resist material.

Pigment dispersion (DP-4): 50.0 parts Pigment dispersion (DP-5): 10.0 parts Acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (manufactured by Shin-Nakamura Chemical Co., Ltd.) "NK ester ATMPT")
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ethylene glycol monomethyl ether acetate: 23.2 parts

(Preparation of green resist material)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a green resist material.

Pigment dispersion (DP-6): 45.0 parts Pigment dispersion (DP-7): 15.0 parts Acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (manufactured by Shin-Nakamura Chemical Co., Ltd.) "NK ester ATMPT")
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ethylene glycol monomethyl ether acetate: 23.2 parts

[Examples 1-8 , Comparative Examples 1-3]

(Example 1; Production of colored composition (DB-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a mixed colored composition.

Triarylmethane salt-forming compound-containing resin solution (DA-1): 2.2 parts Pigment dispersion (DP-1): 8.8 parts Acrylic resin solution: 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49 .0 part

(Example 2-8, Comparative Examples 1-3; coloring composition (DB-2~ 8,14~ 16))
Hereinafter, the colored composition (DB) except that the triarylmethane salt-forming compound-containing resin solution (DA-1) was changed to the triarylmethane salt-forming compound-containing resin solution or the triarylmethane-based compound-containing resin solution shown in Table 3 The colored composition (DB- 2-8, 14-16 ) was produced like 1). However, the pigment dispersion (DP-1) was used in the same manner as in Example 1 in Examples 2 to 8 and Comparative Examples 1 to 3.

(Coating foreign material test method)
The evaluation was performed by preparing a test substrate and counting the number of particles. The coloring composition was applied onto the transparent substrate so that the dried coating film was about 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes to obtain a test substrate. The evaluation was performed using a Olympus system metal microscope “BX60”). The magnification is 500 times, and the number of particles that can be observed in any five fields of view through transmission is counted. In the following evaluation results, ◎ and ○ are good, Δ is a level that does not cause a problem in use although there are many foreign matters, and × indicates coating unevenness (spots) due to foreign matters.

◎: Less than 5 ○: 5 or more, less than 20 △: 21 or more, less than 100 ×: 100 or more

The results are shown in Table 3 below.

When the triarylmethane salt-forming compound (A) is used, in the substrate evaluation, there are few foreign matters (undissolved foreign matter). When the triarylmethane compound (C-1, 2) is used, the foreign matter is There were very many results. For this reason, the product salted with aromatic sulfonic acid (ArSO ₃ ⁻ ) was excellent in preventing the generation of foreign matters. When the triarylmethane compound (C-3) was used, there were few foreign matters.

  [Examples 14 to 28, Comparative Examples 4 to 7]

(Example 14: Resist material (R-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing resist material (R-1).

Colorant dispersion (60 parts in total)
Triarylmethane salt-forming compound-containing resin solution (DA-1): 12.0 parts Pigment dispersion (DP-1): 48.0 parts Acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin Nakamura Chemical "NK Ester ATMPT")
Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.): 1.2 parts sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts ethylene glycol monomethyl ether acetate: 23.2 parts

(Examples 15 to 21 , 27 , 28 , Comparative Examples 4 to 7; Resist material (R-2 to 8, 14 to 19))
Hereinafter, the resist was changed except that the colorant dispersion was changed to the type and blending amount of the colorant dispersion (pigment dispersion or triarylmethane salt-forming compound-containing resin solution or triarylmethane-based compound-containing resin solution) shown in Table 4 In the same manner as the material (R-1), alkali-developable resist materials (R-2 to 8, 14 to 19) were obtained. In the resist material, a colorant dispersion (a pigment dispersion or a triarylmethane salt-forming compound-containing resin solution or a triarylmethane-based compound-containing resin solution) is used in combination, but the total amount of the colorant dispersion is 60 in all resist materials. Part.

(Evaluation of resist material)
Each test of chromaticity, foreign matter, heat resistance, light resistance, and solvent resistance of the coating film of the obtained resist material (R-1 to 8, 14 to 19) was performed by the following methods. The test results are shown in Table 5.

(Coating foreign material test method)
A resist material was applied on the transparent substrate so that the dried coating film became about 2.5 μm, and the whole surface was exposed to ultraviolet light, and then heated in an oven at 230 ° C. for 20 minutes and allowed to cool to obtain an evaluation substrate. The evaluation was performed by observing the surface using a metal microscope “BX60” manufactured by Olympus System. The magnification is 500 times, and the number of particles that can be confirmed in any five visual fields through transmission is counted. In the following evaluation results, ◎ and ○ are good, Δ is a level that does not cause a problem in use although there are many foreign matters, and × indicates coating unevenness due to the foreign matters.

◎: Less than 5 ○: 5 or more, less than 20 △: 20 or more, less than 100 ×: 100 or more

The results are shown in Table 5 below.

(Evaluation of color characteristics)
A resist material was applied on a glass substrate so that x = 0.150 and y = 0.060 using a C light source, and the substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).
The results are shown in Table 5 below.

(Method of coating heat resistance test)
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.5 μm, and after UV exposure through a mask having a predetermined pattern, an alkali developer is sprayed to remove uncured parts. Thus, a desired pattern was formed. Then, after heating in an oven at 230 ° C. for 20 minutes and allowing to cool, the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source is microspectrophotometric. Measurement was performed using a meter (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Further, as a heat resistance test, the sample was heated in an oven at 230 ° C. for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured. The results are shown in Table 5 below.

Using the measured color difference value, the color difference ΔEab * was calculated by the following formula, and the heat resistance of the coating film was evaluated in the following four stages.

ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
◎: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 2.5 Δ: ΔEab * is 2.5 or more and less than 5.0 ×: ΔEab * is 5.0 or more

The results are shown in Table 5 below.

(Method of coating light resistance test)
A test substrate was prepared in the same procedure as the coating heat resistance test, and the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source was measured with a microspectrophotometer (Olympus Optical It measured using "OSP-SP200" by a company. Thereafter, the substrate was placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI) and left for 100 hours. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the light resistance of the coating film was evaluated according to the same criteria as heat resistance. The results are shown in Table 5 below.

(Method of coating solvent resistance test)
A test substrate is prepared in the same procedure as the heat resistance test, and the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd.) It measured using "OSP-SP200"). Thereafter, the substrate was immersed in N-methylpyrrolidone for 30 minutes. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the solvent resistance of the coating film was evaluated according to the same criteria as the heat resistance. The results are shown in Table 5 below.

The resist materials (R-1 to 8, 14) of Examples 14 to 21 and 27 were good in heat resistance, light resistance and solvent resistance. In addition, the resist material (R-15) of Example 28 has excellent color characteristics and results in slightly poor heat resistance, light resistance, and solvent resistance, but has no problem for use in color filters. Met. On the other hand, the resist materials (R-16, 17) of Comparative Examples 4 and 5 have many foreign matters and are difficult to use. In addition, the resist materials (R-16 to 19) of Comparative Examples 4 to 7 had lower brightness (Y) than Examples 14 to 21, 27, and 28. The reason why the brightness (Y) of Comparative Examples 4 to 6 is low is that when the triarylmethane compound used in the resist material itself has low heat resistance, the substrate coated with the resist material is heated at 230 ° C. for 20 minutes. This is probably because the triarylmethane-based compound has already been partially decomposed.

[Examples 29 to 36, 42, 43, Comparative Examples 8 to 11]
(Example 29; color filter (CF-1))
A black matrix was patterned on a glass substrate, and a red resist material was applied on the substrate with a spin coater to a thickness such that x = 0.640 and y = 0.330 to form a colored film. The coating was irradiated with 300 mJ / cm 2 of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. By the same method, the green resist material is formed to have a film thickness such that x = 0.300 and y = 0.600. The green filter segment and the blue filter segment were formed to obtain a color filter (CF-1).

(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained RGB color filter, and a polyimide alignment layer was formed thereon. A polarizing plate was formed on the other surface of this glass substrate. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) glass substrate, and a polarizing plate was formed on the other surface. The two glass substrates prepared in this way are arranged facing each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave After injecting the liquid crystal composition from the opening, the opening was sealed. A liquid crystal display device thus produced was combined with a three-wavelength CCFL light source of a backlight unit to produce a color display device.

(Examples 30-36, 42, 43, Comparative Examples 8-11)
Hereinafter, in the same manner as in Example 29, the color filters of Examples 30 to 36, 42 and 43 and Comparative Examples 8 to 11 (CF-2 to 19) were combined with the resist materials shown in Table 6 and the three-wavelength CCFL light source. A color display device was produced.

Thereafter, in the obtained color display device, a light source was emitted to display a color image, and the brightness of each color filter segment portion was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 6.

When Examples 29 to 36, 42, and 43 (color filter (CF-1 to 8, 14 , 15)) and Comparative Example 11 (color filter (CF-19)) were compared, they were conventionally used for white display. Compared to a color filter (color filter (CF-19)) formed from a resist material containing a copper phthalocyanine pigment and a dioxazine pigment, the resist of the present invention containing a blue pigment and a triarylmethane salt-forming compound (A) High brightness is obtained in color filters (color filters (CF-1 to 8, 14 , 15)) formed from the material. Comparative Examples 8 to 10 (color filters (CF-16 to 18)) are equivalent in lightness to Comparative Example 11 (color filters (CF-19)), and further, Comparative Examples 8 and 9 (color filters (CF--)). 16, 17)), as described above, a large amount of foreign matter is generated. Further, Comparative Examples 8 to 10 (color filters (CF-16 to 18)) have poor heat resistance and light resistance as described above, and are difficult to use practically.

Claims (4)

A blue color composition for a color filter comprising at least a colorant and a resin, wherein the colorant contains a triarylmethane salt forming compound (A) represented by the following general formula (1) and a blue pigment: Blue coloring composition for filters.
General formula (1)

(Wherein R1A to R1D each independently represent a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a benzyl group which may have a substituent). R1A and R1B, and R1C and R1D may each form a ring.
R2 and R3 each independently represent a hydrogen atom or an alkyl group which may have a substituent.
R4 represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X ⁻ represents ArSO ₃ ^— . Ar represents a naphthalene ring substituted benzene ring substituted with -NH _2, or -NH _2. ) The blue coloring composition for a color filter according to claim 1, wherein the blue pigment is a phthalocyanine pigment. The phthalocyanine pigment is C.I. I. The blue coloring composition for a color filter according to claim 2, wherein the pigment is Pigment Blue 15: 6. 4. A color filter comprising at least one red filter segment (pixel), at least one green filter segment (pixel) and at least one blue filter segment (pixel), wherein at least one blue filter segment is according to claims 1-3. A color filter formed from a color filter coloring composition.