JP5573435B2 - Triarylmethane dyes and uses thereof - Google Patents

Description

  The present invention relates to a blue triarylmethane dye suitable for forming a blue filter segment (pixel) of a color filter of a color liquid crystal display device, a color filter coloring composition formed by blending the same, and a color filter coloring composition. The present invention relates to a color filter 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 product of a triarylmethane dye and an aromatic sulfonic acid as a colorant for a color filter (see, for example, Patent Document 3). Even when a color filter was prepared, both heat resistance and light resistance were insufficient.

  Furthermore, as a method for improving the heat resistance, Patent Document 4 proposes that an alkyl group is introduced at the ortho position of the benzene ring of a triarylmethane dye and salted with phthalocyanine sulfonic acid or anthraquinone sulfonic acid as a counter. ing. 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. 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 pamphlet

An object of the present invention is to provide a triarylmethane dye excellent in color characteristics (lightness), heat resistance and light resistance, a color composition for color filters formed by blending the same, and color characteristics (lightness) using the same. It is to provide a color filter having excellent heat resistance and light resistance.

The present inventors have result of extensive studies to solve the above problems, triarylmethane basic dyes and ArSO ₃ obtained by introducing an alkyl group at the ortho position of a benzene ring ^- thoria by salt formation and It has been found that the heat resistance and light resistance of reel methane-based basic dyes can be remarkably improved and high brightness can be maintained.

Due to the effect of introducing an alkyl group at the ortho position of the benzene ring of the triarylmethane dye, the planarity of the dye skeleton was lost, resulting in a structure in which two benzene rings and one naphthalene ring were twisted. Due to this structural change, the physical properties are greatly changed, and the heat resistance and light resistance are improved. Moreover, the dye and ArSO ₃ ^- ones and while maintaining high brightness by salt formation with a very high heat resistance, found that it is possible to realize the light resistance was no the present invention based on this finding It is.

  That is, the present invention relates to a triarylmethane dye for a color filter, which can be represented by the following general formula (1).

General formula (1)

Ｒ２は、未置換の炭素数１〜８のアルキル基を表す。
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。） (Wherein R1A to R1F are each independently a hydrogen atom,
Fluorine atom, chlorine atom, 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, alkyl carboxyl group having 2 to 9 carbon atoms, sulfonic acid amide group, sulfone alkylamide group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, carbon Any one of dialkylaminoethyl group, trifluoromethyl group, trialkylsilyl group having 1 to 8 carbon atoms, nitro group, alkylthio group having 1 to 8 carbon atoms, and vinyl group formed by bonding an alkyl group having 1 to 4 carbon atoms An alkyl group having 1 to 8 carbon atoms which may have a substituent,
Or a fluorine atom, a chlorine atom, a C1-C8 alkyl group, a C1-C8 alkenyl group, a C1-C8 alkoxyl group, a phenyl group, a mesityl group, a tolyl group, a naphthyl group, a cyano group, acetyl An oxy 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, Any of dialkylaminoethyl group, trifluoromethyl group, trialkylsilyl group having 1 to 8 carbon atoms, nitro group, alkylthio group having 1 to 8 carbon atoms, and vinyl group formed by bonding an alkyl group having 1 to 4 carbon atoms in a represent a phenyl group which may have a substituent or, alternatively adjacent R1A and R1B, R1C and R1D, is what R1E and R1F Combined to form a ring shown below.

R2 represents an unsubstituted alkyl group having 1 to 8 carbon atoms.
X ⁻ represents ArSO ₃ ^— . Ar is to display the naphthalene ring substituted substituted benzene ring or -NH _2, with -NH _2. )

The present invention also provides a color composition for a color filter having a colorant carrier comprising at least a transparent resin, a precursor thereof or a mixture thereof and a colorant, wherein the colorant is the above triarylmethane dye. The present invention relates to a color filter coloring composition.

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 as described above. The present invention relates to a color filter formed from a color filter coloring composition.

Triarylmethane for color filters of the present invention having excellent heat resistance and light resistance and high brightness by salt formation with ArSO ₃ ^- and a triarylmethane basic dye having an alkyl group introduced at the ortho position of the benzene ring I was able to obtain the dye. Therefore, when a color filter is prepared with the color filter coloring composition using the coloring matter of the present invention, a color filter having excellent heat resistance, light resistance, and brightness can be formed.

FIG. 1 is an emission spectrum of the backlight used in the examples.

  Hereinafter, the present invention will be described in detail.

The triarylmethane dye of the present invention is represented by the following general formula (1).

General formula (1)

Ｒ２は、未置換の炭素数１〜８のアルキル基を表す。
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。） (Wherein R1A to R1F are each independently a hydrogen atom,
Fluorine atom, chlorine atom, 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, alkyl carboxyl group having 2 to 9 carbon atoms, sulfonic acid amide group, sulfone alkylamide group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, carbon Any one of dialkylaminoethyl group, trifluoromethyl group, trialkylsilyl group having 1 to 8 carbon atoms, nitro group, alkylthio group having 1 to 8 carbon atoms, and vinyl group formed by bonding an alkyl group having 1 to 4 carbon atoms An alkyl group having 1 to 8 carbon atoms which may have a substituent,
Or a fluorine atom, a chlorine atom, a C1-C8 alkyl group, a C1-C8 alkenyl group, a C1-C8 alkoxyl group, a phenyl group, a mesityl group, a tolyl group, a naphthyl group, a cyano group, acetyl An oxy 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, Any of dialkylaminoethyl group, trifluoromethyl group, trialkylsilyl group having 1 to 8 carbon atoms, nitro group, alkylthio group having 1 to 8 carbon atoms, and vinyl group formed by bonding an alkyl group having 1 to 4 carbon atoms in a represent a phenyl group which may have a substituent or, alternatively adjacent R1A and R1B, R1C and R1D, is what R1E and R1F Combined to form a ring shown below.

R2 represents an unsubstituted alkyl group having 1 to 8 carbon atoms.
X ⁻ represents ArSO ₃ ^— . Ar is to display the naphthalene ring substituted substituted benzene ring or -NH _2, with -NH _2. )

If R1A~R1F is an alkyl group or a phenyl group, which may have a substituent is one of these groups may further following substituent group A.

Substituent group A
Fluorine atom, chlorine atom, 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, alkyl carboxyl group having 2 to 9 carbon atoms, sulfonic acid amide group, sulfone alkylamide group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, carbon A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, an alkylthio group having 1 to 8 carbon atoms, and a vinyl group formed by bonding an alkyl group having 1 to 4 carbon atoms.

Among these, the substituents that R1A to R1F have include an alkyl group having 2 to 8 carbon atoms, an alkoxyl group having 2 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, and a sulfone. An acid amide group and a sulfonamide group having 2 to 8 carbon atoms are preferred.

R2 represents an alkyl group having 1 to 8 carbon atoms.

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 dye represented by the general formula (1) is synthesized by refluxing the corresponding benzophenone and the corresponding naphthylamine in toluene in the presence of POCl ₃ , and sodium benzenesulfonate substituted with —NH ₂ — It can be obtained by salt exchange with sodium 1-naphthalenesulfonate substituted with NH ₂ .

General formula (1)

Reference reaction formula

Specific examples of the triarylmethane dye of the present invention include, but are not limited to, the following dyes. Wherein X ^- is ArSO ₃ ^- represents a.

  The coloring composition for a color filter of the present invention may contain a pigment as long as the effects of the present invention are not impaired in order to adjust chromaticity and further improve heat resistance.

  When added to the triarylmethane dye of the present invention, pigments of various colors such as blue, purple and yellow can be used. Examples of the chemical structure include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrene, perylene, rhodamine lake, azo, and aminoketone. In addition, various inorganic pigments can be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The following “CI” means a color index (CI).

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19 and 23, and more preferably C.I. I. Pigment Violet 23.

  Examples of yellow pigments include C.I. I. And CI Pigment Yellow 83, 128, 138, 139, 150, 154, 180, and 185. Of these, C.I. I. Pigment Yellow 138, 139, 150, and 185, and more preferably C.I. I. Pigment yellow 138 and 150.

  In order to maintain sufficient brightness as a coloring component for a color filter, the pigment component is preferably in the range of 500 parts by mass or less with respect to 100 parts by mass of the triarylmethane dye of the present invention. Even if the ratio of the pigment is increased as a whole of the coloring component, the effect of adding the triarylmethane dye of the present invention can be obtained for the purpose of increasing the brightness.

(Miniaturization of pigment)
The pigment that can be used in combination with the coloring composition for a color filter of the present invention can be refined by performing a salt milling process or the like. 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 parts by weight, and most preferably 300 to 1000 parts by weight, based on the total weight of the pigment (100 parts by weight) in terms 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 parts by weight, and most preferably 50 to 500 parts by weight, based on the total weight of the pigment (100 parts 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 parts by weight based on the total weight of the pigment (100 parts by weight).

  It is also preferable to add the triarylmethane dye of the present invention at the same time when the salt is milled (miniaturized). When the pigment is refined, a good colorant can be obtained by adding it together.

(Colorant carrier)
The colorant carrier contained in the coloring composition for a color filter of the present invention is one that disperses a pigment and / or triarylmethane dye, or one that dyes and permeates a dye, and is a transparent resin, its precursor, or those Composed of a mixture of Here, the form of the colorant is composed of a triarylmethane dye, a mixture of a triarylmethane dye and a pigment, or the like.

The transparent resin is a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that are cured by irradiation with active energy rays to form transparent resins, These can be used alone or in admixture of two or more. The colorant carrier is preferably used in an amount of 30 parts by weight or more based on the total weight of the colorant (100 parts by weight) because the film formability and various resistances are good, and the colorant concentration is high and good. It is preferable to use it in an amount of 500 parts by weight or less because it can exhibit excellent color characteristics.

  When the colorant carrier is composed of a mixture of a transparent resin and a precursor thereof, the color filter coloring composition of the present invention can be prepared in the form of a solvent development type or alkali development type color resist. When preparing in the form of an alkali developing type colored resist, an alkali-soluble resin having an acidic group such as a (meth) acrylic acid copolymer resin (alkali-soluble acrylic resin) is used as a part of the colorant carrier.

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

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

  Active energy ray-curable resins include (meth) acrylic compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. Or a resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced by reacting with or cinnamic acid is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

As a monomer or oligomer that is cured by active energy ray irradiation to produce a transparent resin,
Methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, and tricyclodecanyl Monofunctional (meth) acrylates such as (meth) acrylate;
Bifunctional (meth) acrylates such as polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate;

Trifunctional or more polyfunctional compounds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate Functional (meth) acrylate;

1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, and epoxy (meth) acrylate which is a reaction product of an epoxy compound such as phenol novolac resin and (meth) acrylic acid;

Various (meth) acrylic esters modified with polyester, polyurethane, isocyanurate, methylolated melamine, etc .; and

(Meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, etc. Monomers other than acrylates can be used, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

(dispersion)
The coloring composition for a color filter of the present invention is suitably used as a blue coloring composition. It can also be used as a green coloring composition.

  The coloring composition for a color filter of the present invention is dissolved in a colorant carrier composed of the resin, a precursor thereof or a mixture thereof together with a triarylmethane dye or a dye derivative, or the three-roll mill, two It can be produced by finely dispersing using various dispersing means such as a roll mill, a sand mill, a kneader, or an attritor. The color filter coloring composition of the present invention can also be produced by mixing several types of colorants 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. The dispersion aid is excellent in dispersing the colorant and has a great effect of preventing re-aggregation of the colorant after dispersion. Coloring for a color filter in which a colorant is dispersed in a colorant carrier using a dispersion aid. When the composition is used, a color filter having a high spectral transmittance can be obtained.

  Examples of the pigment derivative include a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment (organic pigment, organic dye), anthraquinone, acridone or triazine. It is done.

  In the present invention, a pigment derivative is particularly preferable, and the structure thereof is a compound represented by the following formula (1).

P-Ln Formula (1)

(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 1 part by weight or more, more preferably 3 parts by weight or more, and most preferably 5 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. From the viewpoint of heat resistance and light resistance, the amount is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and most preferably 25 parts by weight or less with respect to 100 parts by weight of the colorant.

  The resin-type dispersant has a colorant-affinity part having the 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.

  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.

(Photopolymerization initiator)
When the colored composition for a color filter of the present invention is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator or the like is added. 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 can be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the colorant in the color filter coloring composition.

(Sensitizer)
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.

  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 photopolymerization initiator contained in the colored composition, and 5 to 50 from the viewpoint of photocurability and developability. More preferably, it is% by weight.

(Other)
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.

(solvent)
In the color composition for color filter of the present invention, a colorant is sufficiently dispersed in a colorant carrier and applied on a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm. In order to make it easier to form, a solvent can be included.

  Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, benzyl alcohol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3 -Butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m -Dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-alkyl Silene, 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 mono Hexyl ether, ethylene glycol monomethyl ether , Ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol 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, dipro Lenglycol 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, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, vinegar Isobutyl, propyl acetate, dibasic esters, and the like.

  Among them, glycolate such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate because the triarylmethane dye of the present invention has good dispersibility and solubility. Preferably, ketones such as cyclohexanone and aromatic alcohols such as benzyl alcohol are used.

  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 for a color filter to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, the total weight of the colorant is based on (100 parts by weight), and 800 to It is preferably used in an amount of 8000 parts by weight.

(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 coloring composition for a color filter 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 is preferably used in an amount of 0.003 to 0.5 parts by weight based on the total weight (100 parts by weight) of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. 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 for color filters 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 coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. 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 parts by weight with respect to 100 parts by weight of the colorant in the color filter coloring composition.

  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 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the color filter coloring composition.

(Removal of coarse particles)
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that the coloring composition for color filters substantially does not contain particles of 0.5 μm or more. 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 is a color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein at least one blue filter segment is colored for the color filter of the present invention. It is formed using a composition.

  The color filter of the present invention is a color filter including at least one magenta color filter segment, at least one cyan color filter segment, and at least one yellow color filter segment. It is formed with the coloring composition for color filters of the invention.

  The red filter segment can be formed using a normal red coloring composition containing a red pigment and a pigment 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, or may be used in combination of a yellow pigment 214, and the like. In addition, a basic dye or an acid dye exhibiting orange and / or yellow can be used in combination.

  The green filter segment can be formed using a normal green coloring composition including a green pigment and a pigment carrier. Examples of the green pigment include C.I. I. Pigment Green 2, 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, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 and the like. Further, a basic dye or an acid dye exhibiting yellow can be used in combination.

  The magenta color filter segment can be formed using a normal magenta color coloring composition including a magenta color pigment and a pigment carrier. Examples of the magenta coloring composition include C.I. I. Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 192, 202, 207, 209, C.I. I. Pigment Violet 19 or the like is used. In addition, a basic dye or an acid dye exhibiting a magenta color can also be used.

  The yellow filter segment can be formed using a normal yellow coloring composition containing a yellow pigment and a pigment carrier. As a yellow pigment, the pigment illustrated as a yellow pigment which can be used together with a red pigment or a green pigment can be used. Further, a basic dye or an acid dye exhibiting yellow can also be used.

(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 forming a filter segment by a photolithography method, the color composition for color filter prepared as the solvent development type or alkali development type coloring resist is spray coated, spin coated, slit coated, roll coated, etc. on a transparent substrate. The coating method is applied so that the dry film thickness is 0.2 to 5 μm. 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, 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 a 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 for producing a color filter by patterning a coloring composition for a color filter by an inkjet method.

  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”.

Example 1

(Synthesis of Compound 1)
To a mixture of 12.5 parts of 4-dimethylaminobenzoic 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 the dropwise addition, the mixture was stirred for 15 minutes, 10.5 parts of N, N-dimethyl-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 1 was obtained. The yield was 36.0%.

(Synthesis of Compound 2)
5 parts of Compound 1 and 3.0 parts of N, N-dimethyl-1-naphthylamine (Tokyo Chemicals) were dissolved in 20 parts of toluene, 3.4 parts of phosphorus oxychloride was added, and the mixture was refluxed for 3 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., 6.9 parts of Compound 2 was obtained. The yield was 82.2%.

(Synthesis of Compound 3)
Compound 2 (1.20 part), 2-aminobenzenesulfonic acid (Tokyo Chemicals) (1.00 part), sodium hydroxide (0.128 part), dichloromethane (130 parts), and water (200 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 0.97 parts of compound 3. The yield was 62.7%.

Example 2

(Synthesis of Compound 4)
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 4 was obtained. The yield was 35.2%.

(Synthesis of Compound 5)
5 parts of Compound 4 and 2.9 parts of N, N-diethyl-1-naphthylamine (Tokyo Chemicals) were dissolved in 20 parts of toluene, 3.6 parts of phosphorus oxychloride was added, and the mixture was refluxed for 3 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., 6.9 parts of Compound 5 was obtained. The yield was 83.6%.

(Synthesis of Compound 6)
The compound 5 was synthesized in the same manner as the compound 3 of Example 1 except that 1.20 parts, sodium 2-aminobenzenesulfonate (Tokyo Chemicals) was changed to 2.42 parts, and sodium hydroxide was 1.30 parts. 1.28 parts of compound 6 were obtained. The yield was 78.8%.

Example 3

(Synthesis of Compound 7)
5 parts of compound 4 and 2.6 parts of N-ethyl-1-naphthylamine (Tokyo Chemicals) were dissolved in 20 parts of toluene, 3.4 parts of phosphorus oxychloride was added, and the mixture was refluxed for 3 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., 6.5 parts of Compound 7 was obtained. The yield was 88.2%.

(Synthesis of Compound 8)
The compound 7 was synthesized in the same manner as Compound 3 in Example 1, except that the amount was changed to 1.25 parts of Compound 7, 2.41 parts of sodium 2-aminobenzenesulfonate (Tokyo Chemicals) and 1.30 parts of sodium hydroxide. 1.34 parts of compound 8 were obtained. The yield was 74.8%.

Example 7

(Synthesis of Compound 12)
1.20 parts of compound 7 and 2.79 parts of sodium 2-aminonaphthalenesulfonate (Tokyo Kasei), 130 parts of dichloromethane and 200 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 1.17 parts of compounds 12. The yield was 72.0%.

Example 8

(Synthesis of Compound 13)
A mixture of 20 parts of m-toluidine (Tokyo Chemicals), 63.9 parts of n-butyl iodide, 64.5 parts of calcium carbonate and 220 parts of N-methylpyrrolidone was stirred at 120 ° C. for 3 hours and then at 140 ° C. for 15 hours. did. After cooling to room temperature, the reaction solution and 360 parts of toluene were added to another container and filtered. The filtrate was washed three times with water, the toluene layer was extracted, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (hexane / ethyl acetate = 20/1) and dried under reduced pressure at 60 ° C. to obtain 29.2 parts of compound 12. The yield was 71.3%.

(Synthesis of Compound 14)
Add 9.5 parts of anhydrous aluminum chloride and 14 parts of 1,2-dichloroethane, cool in an ice bath, and add dropwise 13.0 parts of 4-bromobenzoic acid chloride (Tokyo Chemicals) in 25 parts of 1,2-dichloroethane. did. After stirring for 30 minutes, a solution of 13.0 parts of Compound 13 in 25 parts of 1,2-dichloroethane was added dropwise, and the mixture was stirred for 1 hour and further stirred at room temperature for 3 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 = 10/1). After drying under reduced pressure at 60 ° C., 12.3 parts of Compound 14 was obtained. The yield was 51.5%.

(Synthesis of Compound 15)
Compound 14 12.3 parts, di-n-butylamine 7.9 parts, t-butoxy sodium 5.9 parts, palladium (II) acetate 0.4 parts and tri-t-butylphosphine 0.7 parts The solution was dissolved in a portion and refluxed for 7 hours. After cooling to room temperature, 50 parts of water was added to extract the organic layer. 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 = 7/1). After drying under reduced pressure at 60 ° C., 5.2 parts of Compound 15 were obtained. The yield was 37.7%.

(Synthesis of Compound 16)
3.2 parts of Compound 15 and 1.2 parts of N-ethyl-1-naphthylamine (Tokyo Chemicals) were dissolved in 10 parts of toluene, 1.6 parts of phosphorus oxychloride was added, and the mixture was refluxed for 3 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 at 60 ° C. under reduced pressure, 3.5 parts of compound 16 was obtained. The yield was 81.1%.

(Synthesis of Compound 17)
The compound 16 was synthesized in the same manner as the compound of Example 1, except that 1.10 parts, sodium 2-aminobenzenesulfonate (Tokyo Chemicals) 2.22 parts, and sodium hydroxide 1.30 parts. 1.38 parts of compound 17 were obtained. The yield was 83.8%.

Example 9

(Synthesis of Compound 18)
The synthesis was carried out in the same manner as in Example 7, except that the compound 16 was changed to 1.20 parts and 1.34 parts of sodium 1-naphthalenesulfonate (Tokyo Chemicals). 1.26 parts of compound 18 were obtained. The yield was 83.2%.

Example 10

(Synthesis of Compound 19)
Add 9.5 parts of anhydrous aluminum chloride and 14 parts of 1,2-dichloroethane, cool in an ice bath, and add dropwise 13.0 parts of 4-bromobenzoic acid chloride (Tokyo Chemicals) in 25 parts of 1,2-dichloroethane. did. After stirring for 30 minutes, a solution of 13.0 parts of 3-bromotoluene in 25 parts of 1,2-dichloroethane was added dropwise, stirred for 1 hour, and further stirred at room temperature for 3 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 = 10/1). After drying under reduced pressure at 60 ° C., 12.3 parts of Compound 19 was obtained. The yield was 51.5%.

(Synthesis of Compound 20)
Compound 19 12.3 parts, diisobutylamine 7.9 parts, t-butoxy sodium 5.9 parts, palladium (II) acetate 0.4 parts and tri-t-butylphosphine 0.7 parts in dehydrated toluene 90 parts Dissolved and refluxed for 7 hours. After cooling to room temperature, 50 parts of water was added to extract the organic layer. 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 = 7/1). After drying under reduced pressure at 60 ° C., 5.2 parts of compound 20 were obtained. The yield was 37.7%.

(Synthesis of Compound 21)
5 parts of compound 20 and 1.2 parts of N-ethyl-1-naphthylamine (Tokyo Chemicals) were dissolved in 10 parts of toluene, 1.6 parts of phosphorus oxychloride was added, and the mixture was refluxed for 3 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., 3.5 parts of compound 21 were obtained. The yield was 81.1%.

(Synthesis of Compound 22)
Compound 21 was synthesized in the same manner as Compound 3 in Example 1, except that 1.20 parts, sodium 2-aminobenzenesulfonate (Tokyo Chemicals) 2.72 parts, and sodium hydroxide 1.50 parts were used. 1.20 parts of compound 22 were obtained. The yield was 78.8%.

Example 11

(Synthesis of Compound 23)
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 the dropwise addition, the mixture was stirred for 15 minutes, 14.2 parts of Compound 13 was dropped, the temperature was returned to room temperature, and the mixture was 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). After drying under reduced pressure at 60 ° C., 11.8 parts of Compound 23 was obtained. The yield was 46.3%.

(Synthesis of Compound 24)
5.8 parts of compound 23 and 2.5 parts of N-ethyl-1-naphthylamine (Tokyo Chemicals) were dissolved in 20 parts of toluene, 3.4 parts of phosphorus oxychloride was added, and the mixture was refluxed for 3 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 24 was obtained. The yield was 73.8%.

(Synthesis of Compound 25)
The compound 24 was synthesized in the same manner as the compound 3 of Example 1, except that 1.20 parts, sodium 2-aminobenzenesulfonate (Tokyo Chemicals) 2.72 parts, and sodium hydroxide 1.50 parts were used. 1.28 parts of compound 20 were obtained. The yield was 78.8%.

Example 12

(Synthesis of Compound 26)
A mixture of 20 parts of 3-ethylaniline (Tokyo Chemicals), 68.9 parts of n-ethyl iodide, 64.5 parts of calcium carbonate, and 220 parts of N-methylpyrrolidone was stirred at 120 ° C. for 3 hours and then at 140 ° C. for 15 hours. Stir. After cooling to room temperature, the reaction solution and 360 parts of toluene were added to another container and filtered. The filtrate was washed three times with water, the toluene layer was extracted, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (hexane / ethyl acetate = 20/1) and dried under reduced pressure at 60 ° C. to obtain 27.2 parts of compound 26. The yield was 74.4%.

(Synthesis of Compound 27)
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 the dropwise addition, the mixture was stirred for 15 minutes, and 11.2 parts of Compound 26 were added dropwise. The mixture was 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., 8.7 parts of Compound 27 was obtained. The yield was 37.2%.

(Synthesis of Compound 28)
5 parts of Compound 27 and 2.5 parts of N-ethyl-1-naphthylamine (Tokyo Chemicals) were dissolved in 20 parts of toluene, 3.4 parts of phosphorus oxychloride was added, and the mixture was refluxed for 3 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., 7.0 parts of compound 28 were obtained. The yield was 84.2%.

(Synthesis of Compound 29)
The compound 28 was synthesized in the same manner as the compound 3 of Example 1, except that 1.20 parts, sodium 2-aminobenzenesulfonate (Tokyo Chemicals) 2.22 parts and sodium hydroxide 1.50 parts were used. 1.38 parts of compound 29 were obtained. The yield was 74.8%.

Example 13

(Synthesis of Compound 30)
Compound 19 12.3 parts, aniline 8.9 parts, tert-butoxy sodium 5.9 parts, palladium (II) acetate 0.4 parts, and tri-t-butylphosphine 0.7 parts are dissolved in dehydrated toluene 90 parts. And refluxed for 7 hours. After cooling to room temperature, 50 parts of water was added to extract the organic layer. 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 = 7/1). After drying under reduced pressure at 60 ° C., 6.2 parts of Compound 30 was obtained. The yield was 32.7%.

(Synthesis of Compound 31)
5 parts of compound 30 and 2.5 parts of N-phenyl-1-naphthylamine (Tokyo Chemicals) were dissolved in 20 parts of toluene, 3.4 parts of phosphorus oxychloride was added, and the mixture was refluxed for 3 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., 7.9 parts of Compound 31 was obtained. The yield was 88.8%.

(Synthesis of Compound 32)
The compound 31 was synthesized in the same manner as in Example 1 except that 1.20 parts, sodium 2-aminobenzenesulfonate (Tokyo Chemicals) 2.62 parts, and sodium hydroxide 1.50 parts were used. 1.30 parts of compound 32 were obtained. The yield was 78.8%.

Comparative Example 1

  C. I. We used Basic Blue 7 (Tokyo Chemicals).

Comparative Example 2

(Dye synthesis)
C. I. 1.20 parts of Basic Blue 7 (Tokyo Chemicals), 2.54 parts of sodium benzenesulfonate, 130 parts of dichloromethane and 200 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 0.97 part pigment | dye. The yield was 62.7%.

Comparative Example 3

(Dye synthesis)
C. I. 1.20 parts of Basic Blue 7 (Tokyo Chemicals), 2.54 parts of sodium 1-naphthalenesulfonate, 130 parts of dichloromethane, and 200 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 0.97 part pigment | dye. The yield was 62.7%.

実施例３の中間体である化合物７を使用した。 Comparative Example 4

Compound 7 which is an intermediate of Example 3 was used.

Comparative Example 5

  C. I. 1.20 parts of Basic Blue 7 (Tokyo Chemicals) was dissolved in 130 parts of dichloromethane, and then mixed with 0.10 parts of NaOH and 1.64 parts of phthalocyanine sulfonic acid in 200 parts of water, 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 2.27 parts of pigment | dyes. The yield was 84.8%.

Comparative Example 6

  Compound 7 (1.20 part) was dissolved in dichloromethane (130 parts). To this, 200 parts (water) dissolved in NaOH (0.10 part) and phthalocyanine sulfonic acid (1.64 part) 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 2.27 parts of pigment | dyes. The yield was 84.8%.

(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 further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight 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.

  Here, the polymerization average molecular weight (Mw) of the acrylic resin was measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. The weight average molecular weight (Mw) in terms of polystyrene.

(Preparation of colored composition 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. The colored composition 1 was produced by filtration using a filter.
Triarylmethane Example 1 Dye: 11.0 parts Prepared acrylic resin solution: 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin-type dispersant (EFKA4300): 1.0 parts

(Preparation of colored compositions 2 , 3, 7-24)
Hereinafter, colored compositions 2 , 3, 7 to 24 were produced in the same manner as colored composition 1, except that the triarylmethane Example 1 dye was replaced with the triarylmethane dye shown in Table 1.

Table 1

(Adjustment of resist material 1)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain an alkali developing resist material (resist material 1).
Coloring composition 1: 60.0 parts Acrylic resin solution prepared previously: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
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 Propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts

(Adjustment of resist materials 2 , 3, 7 to 21)
Hereinafter, alkali-developable resist materials 2 , 3, 7 to 21 were obtained in the same manner as the resist material 1 except that the colored composition 1 was replaced with the colored composition shown in Table 2.

Table 2

[Examples 14-16 , 20-29 , 33-39 , Comparative Examples 7-15: Evaluation of resist material]
The obtained resist materials 1 to 3 and 7 to 19 were subjected to heat resistance, light resistance, and tests by the following methods.

(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 UV exposure is performed through a mask having a predetermined pattern, and then an alkali developer is sprayed to remove uncured portions. Thus, a desired pattern was formed. Then, after heating in an oven at 110 ° C. for 20 minutes and allowing to cool, the color difference 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source was measured with a microspectrophotometer. (Olympus Optical Co., Ltd. “OSP-SP200”). Further, as a heat resistance test, it was heated in an oven at 200 ° C. for 20 minutes, and a color difference 2 (L * (2), a * (2), b * (2)) with a C light source was measured.

Using the measured color difference value, the color difference change rate ΔEab was calculated by the following formula, and the heat resistance of the coating film was evaluated.

ΔEab = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

(Method of coating light resistance test)
A test substrate was prepared in the same procedure as the coating film heat resistance test, and a UV cut film was attached to the substrate. Color difference 1 (L * (1), a * (1), b * (1)) with a C light source was measured using a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Thereafter, the substrate was placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI) and left for 100 hours. After removing the substrate, the color difference 2 (L * (2), a * (2), b * (2)) with C light source is measured, and the color difference change rate ΔEab is calculated in the same manner as in the coating heat resistance test. did.

  Table 3 shows the results of the coating heat resistance and light resistance test.

Table 3

When comparing Examples 14 to 16 , 20 to 26, Comparative Examples 8 and 9 and Comparative Examples 7 and 10 in Table 3, the color difference ΔEab before and after the heat resistance and light resistance tests was obtained by salt exchange of Cl ⁻ to ArSO 3 ⁻ . It is small in Examples 14 to 26 and Comparative Examples 8 and 9 using a dye. From this fact, it can be seen that both heat resistance and light resistance are improved by salt exchange of Cl ⁻ to ArSO 3 ⁻ .

However, in Comparative Examples 8 and 9, ΔEab is 10 or more and less than ΔEab = 5 which is a practical level, both the heat resistance and the light resistance are not far. On the other hand, Me groups were introduced at the ortho positions of the benzene ring, and the primary amino group was introduced as a substituent for ArSO3 ⁻ , the ΔEab in Examples 14 to 16 and Examples 20 to 26 was 3 or less, and heat resistance and light resistance sex is above direction.

Further, when Comparative Example 11 and Comparative Example 12 using a salt-forming dye with phthalocyanine sulfonic acid are compared, Comparative Example 12 has a heat resistance and light resistance due to the introduction of a methyl group at the ortho position of the benzene ring of the dye skeleton. It has improved. However, since the effect is small, the heat resistance and light resistance of Examples 14 to 16, 20 to 26 levels are not obtained.

(Evaluation of color characteristics (lightness))
The resist materials 1 to 3, 7 to 13, 18, 19, and 21 are mixed with the resist material 20 so as to have a constant hue, and x = 0.150 in a C light source on the glass substrate. A resist material was applied to a film thickness such that y = 0.06, and the substrate was heated at 110 ° C. for 20 minutes. Thereafter, the brightness of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

  Table 4 shows the results of the color characteristic (lightness) test.

Table 4

In Examples 27 to 29, 33 to 39, it was possible to obtain high brightness as compared with Comparative Example 15 containing a copper phthalocyanine pigment and a dioxazine pigment, which were conventionally used suitably. Further, even when compared with Comparative Examples 13 and 14 which are salt-forming dyes with phthalocyanine sulfonic acid, a clearly high brightness was obtained.

[Examples 40 and 41 and Comparative Examples 16 and 17: Evaluation of color filters]
(Adjustment of Example 40)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain an alkali developing resist material 22.
Coloring composition 22: 50.0 parts Coloring composition 23: 10.0 parts The previously prepared acrylic resin solution: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts ("NK ester ATMPT made by Shin-Nakamura Chemical Co., Ltd.) ")
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 Propylene glycol monomethyl ether acetate (PGMAC): 23 .2 parts

(Adjustment of resist materials 23 to 27)
Hereinafter, alkali-developing resist materials 23 to 27 were obtained in the same manner as the resist material 22 except that the coloring compositions 22 and 23 were changed to the coloring compositions and blending amounts shown in Table 5. The total amount of the coloring composition is 60 parts in all resist materials.

Table 5

  A color filter was produced using the obtained resist material, and its quality was confirmed. First, a method for manufacturing a color filter will be described.

(Production of color filter)
A black matrix is patterned on a glass substrate, and a red resist material (resist material 22) is applied to the substrate with a spin coater in a C light source (hereinafter also used for green and blue) x = 0.640, y = 0. The film was applied to a film thickness of 330 to form a colored film. The film was irradiated with ultraviolet rays of 300 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development is performed with an alkali developer composed of a 2% by weight aqueous sodium carbonate solution to remove unexposed portions, and then the substrate is washed with ion-exchanged water. The substrate is heated at 230 ° C. for 20 minutes to form a red filter segment. did. By the same method, the green resist material (resist material 23) is formed to have a film thickness such that x = 0.300 and y = 0.600, and the blue resist material (resist material 24) is used. Each was applied to a thickness such that y = 0.06 to form a green filter segment and a blue filter segment to obtain a color filter.

(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained 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. The liquid crystal display device thus produced was combined with a backlight unit to obtain a liquid crystal panel (Example 14).

  Thereafter, the color filters and color liquid crystal devices of Examples 14 and 15 and Comparative Examples 7 and 8 were produced using the resist materials shown in Table 6 by the same method. The emission spectrum of the backlight used is shown in FIG.

Table 6

  Thereafter, in the obtained color display device, a light source is emitted to display a color image, and the brightness of the red, green, and blue filter segment portions is measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.) The brightness of white display in the color filter was obtained from the obtained brightness. The results are shown in Table 7.

Table 7

  Comparing Examples 40 and 41 with Comparative Example 17, compared with a color filter using a resist material containing a copper phthalocyanine pigment and a dioxazine-based pigment that has been conventionally used favorably in a blue filter segment, triarylmethane and benzenesulfone High brightness was obtained in a color filter using a resist material containing a salt forming dye with acid or naphthalenesulfonic acid.

  In addition, since the color filter of Comparative Example 16 uses a resist material containing a salt-forming pigment of triarylmethane and phthalocyanine sulfonic acid as a colorant, higher brightness is obtained than the color filter of Comparative Example 17. As described above, this resist material is inferior in resistance and lighter than in Examples 40 and 41.

  From the above, the color characteristics (lightness), heat resistance, and light fastness can be obtained by using the salt-forming dyes of the triarylmethane dyes having an alkyl group introduced at the ortho position of the benzene ring and the specific arylsulfonic acid of the present invention. It becomes possible to obtain an excellent coloring composition for a color filter and a color filter.

Claims (3)

A triarylmethane dye for a color filter represented by the following general formula (1):
General formula (1)

(Wherein R1A to R1F are each independently a hydrogen atom,
Fluorine atom, chlorine atom, 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, alkyl carboxyl group having 2 to 9 carbon atoms, sulfonic acid amide group, sulfone alkylamide group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, carbon Any one of dialkylaminoethyl group, trifluoromethyl group, trialkylsilyl group having 1 to 8 carbon atoms, nitro group, alkylthio group having 1 to 8 carbon atoms, and vinyl group formed by bonding an alkyl group having 1 to 4 carbon atoms An alkyl group having 1 to 8 carbon atoms which may have a substituent,
Or a fluorine atom, a chlorine atom, a C1-C8 alkyl group, a C1-C8 alkenyl group, a C1-C8 alkoxyl group, a phenyl group, a mesityl group, a tolyl group, a naphthyl group, a cyano group, acetyl An oxy 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, Any of dialkylaminoethyl group, trifluoromethyl group, trialkylsilyl group having 1 to 8 carbon atoms, nitro group, alkylthio group having 1 to 8 carbon atoms, and vinyl group formed by bonding an alkyl group having 1 to 4 carbon atoms in a represent a phenyl group which may have a substituent or, alternatively adjacent R1A and R1B, R1C and R1D, is what R1E and R1F Combined to form a ring shown below.

R2 represents an unsubstituted alkyl group having 1 to 8 carbon atoms.
X ⁻ represents ArSO ₃ ^— . Ar is to display the naphthalene ring substituted substituted benzene ring or -NH _2, with -NH _2. ) A color composition for a color filter having a colorant carrier comprising at least a transparent resin, a precursor thereof or a mixture thereof and a colorant, wherein the colorant is the triarylmethane dye according to claim 1 Coloring composition for filters. 3. 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 the at least one blue filter segment is a color filter according to claim 2. A color filter formed from a coloring composition for use.

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