JP4419547B2 - Coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a colored composition for a color filter used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter formed using the same.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the 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.
On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

Therefore, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used. The color filter is mainly produced by the following two methods. Is manufactured.
In the first method, a dispersion of a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, the solvent is removed by drying, a pattern exposure of one filter color is performed, and then an unexposed portion is obtained. The color filter can be manufactured by repeating the same operation for all the filter colors in order after forming a first color pattern by applying a process such as heating if necessary.

In the second method, a dispersion of a pigment in a transparent resin solution is applied to a transparent substrate such as glass, the solvent is removed by drying, and then a resist such as a positive resist is applied on the coating film. Two filter color patterns are exposed and developed to form a resist pattern. Using this as an etching resist, the pigment-dispersed coating film without the resist pattern is removed with an etching solution, and the resist coating film is peeled off. A pattern of colored eyes is formed. A color filter can be manufactured by repeating the same operation sequentially for all the filter colors after applying a treatment such as heating if necessary. Note that the development of the resist and the etching of the pigment-dispersed coating film can be performed simultaneously.
In the above method, a colored composition containing a yellow pigment is used for the production of the green filter segment, and conventionally CI Pigment Yellow 139, CI Pigment Yellow 185 and the like have been used as yellow pigments. (For example, refer to Patent Document 1).
JP 2001-249216 A

However, in the situation where there is an increasing demand for color characteristics such as transparency, that is, brightness, improvement in color purity, coating uniformity when forming pixels, sensitivity, developability, pattern shape, etc. CI Pigment Yellow 139 and the like adopted from No. 1 are becoming difficult to deal with. In particular, in recent years, liquid crystal display devices have been applied to TV monitor applications, and in order to produce a panel with low power consumption, a bright color filter, that is, a white light having a high brightness and a good color temperature is required.
Accordingly, an object of the present invention is to provide a green coloring composition which is excellent in color characteristics, has a particularly high transmittance, and can thus form a white color filter having a high brightness. Another object of the present invention is to provide a color filter having good color characteristics.

［Ｒ₁、Ｒ₂は、それぞれ独立に、ＣＮまたはＣＯＮＨＣＨ₃を表す。］
一般式（２）

［Ｙは、Ｃｕ、Ｋ、Ｃａ、Ｎａ、Ｎｉ、Ｆｅ、Ａｌ、Ｃｏ、またはＳを表す。］
一般式（３）

［Ｘ₁〜Ｘ₁₆は、それぞれ独立に、Ｈ、Ｆ、Ｃｌ、Ｂｒ、またはＩを表す。Ｚは、Ｃｕ、Ｋ、Ｃａ、Ｎｉ、Ｆｅ、Ａｌ、Ｃｏ、またはＳを表す。］
The coloring composition for a color filter of the present invention includes a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture thereof, an isoindoline pigment represented by the following general formula (1), and the following general formula (2). Containing the azo pigment represented by a weight ratio of 34.7: 65.3-98.3: 1.7, and further including a phthalocyanine pigment represented by the following general formula (3): Is the most important feature.
General formula (1)

[R ₁ and R ₂ each independently represents CN or CONHCH ₃ . ]
General formula (2)

[Y represents Cu, K, Ca, Na, Ni, Fe, Al, Co, or S. ]
General formula (3)

[X _{1 to} X ₁₆ each independently represent H, F, Cl, Br, or I. Z represents Cu, K, Ca, Ni, Fe, Al, Co, or S. ]

  Further, the color filter of the present invention comprises at least one red filter segment, at least one blue filter segment, and at least one green filter segment, and the at least one green filter segment is formed from the colored composition. It is characterized by.

  Since the coloring composition for a color filter of the present invention contains a specific green pigment and two kinds of yellow pigments, the spectral characteristics are efficiently adjusted. By forming a green filter segment using the coloring composition, In a color filter having red, green and blue filter segments, the brightness of white can be increased without changing the color temperature.

The coloring composition for a color filter of the present invention comprises a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture thereof, an isoindoline pigment represented by the general formula (1) dispersed in the pigment carrier, and a general formula The azo pigment represented by (2) in a weight ratio of 34.7: 65.3 to 98.3: 1.7, and a phthalocyanine pigment represented by the general formula (3): It is characterized by combining a specific green pigment and two kinds of yellow pigments.
The reason for combining the specific green pigment and the two kinds of yellow pigments is to effectively combine the transmission spectra of the respective pigments so as to exhibit the maximum performance. By combining a specific green pigment and two yellow pigments, the transmission region of the spectral spectrum is expanded, and the brightness as white can be increased.

As the isoindoline pigment represented by the general formula (1), CI Pigment Yellow 185 is preferable from the viewpoint of hue and spectral characteristics.
Examples of the azo pigment represented by the general formula (2) include CI Pigment Yellow 150, CI Pigment Yellow 13, and the like, and CI Pigment Yellow 150 is preferable in terms of hue, spectral characteristics, heat resistance, and weather resistance.
Examples of the phthalocyanine pigment represented by the general formula (3) include CI Pigment Green 36, CI Pigment Green 7, Pigment Green 37, and Pigment Blue 15. From the viewpoint of hue and spectral characteristics, CI Pigment Green 36 or CI Pigment Green 7 is used. preferable.

The isoindoline pigment represented by the general formula (1) and the azo pigment represented by the general formula (2) are contained in a weight ratio of 34.7: 65.3 to 98.3: 1.7. Is done. If the amount of the isoindoline pigment represented by the general formula (1) is less than the above range, the lightness of white cannot be sufficiently increased due to the spectral characteristics of the pigment. This is because the brightness of white does not increase sufficiently.

Further, the isoindoline pigment represented by the general formula (1) and the azo pigment represented by the general formula (2) are in total with respect to 100 parts by weight of the phthalocyanine pigment represented by the general formula (3). And it is preferable to contain in the ratio of 30-120 weight part. If the total amount of the isoindoline pigment represented by the general formula (1) and the azo pigment represented by the general formula (2) is less than the above range, the green color becomes strong and the white color temperature is excessively increased. The white xy shifts, and conversely, if it is larger than the above range, the yellowish color becomes strong, and the white color temperature decreases too much, causing the white xy to shift.
The above isoindoline pigment, azo pigment, and phthalocyanine pigment may be refined by salt milling, acid pasting, or the like.

The coloring composition has titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red pepper (in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness ( Inorganic pigments such as red iron (III) oxide, cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black can be included.
The coloring composition can be produced by mixing three kinds of pigments and then finely dispersing the obtained pigment mixture in a pigment carrier by a known method. The colored composition can also be produced by mixing finely dispersed pigments in a pigment carrier.

The coloring composition preferably contains a dye derivative because the pigment dispersibility is improved by including the dye derivative.
A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called dyes. Examples of the dye derivatives 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. You can use what you have. In particular, a pigment derivative having a basic group and a triazine derivative having a basic group are preferably used because they have a large pigment dispersion effect.

一般式（６）

一般式（７）

一般式（８）

Specific examples of the basic group possessed by the dye derivative and the triazine derivative include substituents represented by the following general formulas (5), (6), (7) and (8).
General formula (5)

General formula (6)

General formula (7)

General formula (8)

[Wherein, X represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ : each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or a combination of R ₁ and R ₂ Represents an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom.
R _{3 represents} an alkyl group which may be substituted, an alkenyl group which may be substituted or a phenyl group which may be substituted.
R ₄ , R ₅ , R ₆ , R ₇ : each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group.
Y: represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group.
Z: represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted phenylene group.
P: The substituent represented by General formula (9) or the substituent represented by General formula (10) is represented.
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the general formula (9) or a substituent represented by the general formula (10). ]

一般式（１０）

General formula (9)

General formula (10)

  Examples of the organic dye constituting the dye derivative having a basic group include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, Anthraquinone dyes such as anthrone, indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, sulene System dyes and metal complex dyes. Moreover, the organic pigment illustrated later may be sufficient.

  Triazines constituting triazine derivatives having basic groups are alkyl groups such as methyl and ethyl groups, amino groups or dimethylamino groups, alkylamino groups such as diethylamino groups and dibutylamino groups, nitro groups, hydroxyl groups and methoxy groups. Group, alkoxy group such as ethoxy group and butoxy group, halogen such as chlorine or methyl group, methoxy group, amino group, dimethylamino group, phenyl group which may be substituted with hydroxyl group, methyl group, ethyl group, methoxy group 1,3,5-triazine which may have a substituent such as phenylamino group which may be substituted with ethoxy group, amino group, dimethylamino group, diethylamino group, nitro group, hydroxyl group and the like.

The pigment derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the following formulas (11) to (14) into an organic dye, it reacts with the substituent to form a substituent represented by the general formulas (5) to (8). Amine components such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazine- It can be obtained by reacting 2-ylamino] aniline or the like.
Formula (11) -SO ₂ Cl
Formula (12) -COCl
Equation (13) -CH ₂ NHCOCH ₂ Cl
Equation (14) -CH ₂ Cl

When the organic dye is an azo dye, the basic group is introduced by introducing a substituent represented by the general formulas (5) to (8) into the diazo component or the coupling component in advance and then performing a coupling reaction. An azo pigment derivative having the same can also be produced.
The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, an amine component starting from cyanuric chloride and forming a substituent represented by the general formulas (5) to (8) on at least one chlorine of cyanuric chloride, for example, N, N-dimethylaminopropylamine or N It is obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  Examples of the amine component used for forming the substituents represented by the general formulas (5) to (10) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine. N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, di Butylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, Didecylamine, diallylamine, , N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethyl Aminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-lauryl amino Lopylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecholine, 4 -Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isnicopetinate, Ethyl isonicopetic acid, 2-Piperidinethanol, Pyrrolidine, 3-hydroxy Pyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-pipecholine, N-amino Nopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

As the pigment derivative, those shown in Tables 1 to 9 can be used, but are not limited thereto. The pigment derivatives can be used alone or in admixture of two or more.
In the coloring composition, the pigment and the dye derivative or the triazine derivative are usually in a weight ratio of 50:50 to 99.5: 0.5, preferably 70:30 to 99: 1, more preferably 75:25 to 98: 2. More preferably, it is contained in a ratio of 80:20 to 97: 3. If the amount of the dye derivative or the triazine derivative is less than the above range, the pigment dispersion stabilizing effect is not exhibited, and conversely if more than the above range, the hue of the filter segment may change undesirably, In addition, the manufacturing cost increases.

As described above, the pigment carrier in which the three kinds of pigments are dispersed is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a 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. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and its precursor includes a monomer or an oligomer that is cured by irradiation with radiation to form a transparent resin. Alternatively, two or more kinds can be mixed and used.
When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the colored composition for a color filter of the present invention.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer 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.

  The pigment carrier preferably contains a transparent resin obtained by copolymerizing the compound (a) represented by the general formula (4) and another compound (b) having an ethylenically unsaturated double bond. Since the transparent resin exhibits an excellent dispersion effect for almost all pigments, it functions to prevent the pigments from agglomerating in the coloring composition and to maintain a finely dispersed state of the pigments. Therefore, when a filter segment is formed using the colored composition of the present invention obtained by dispersing three kinds of pigments on a pigment carrier containing the transparent resin, a filter segment with less pigment aggregates can be formed. A color filter with high transmittance and high color purity can be produced.

（Ｒ₁は、ＨまたはＣＨ₃、Ｒ₂はアルキレン基、Ｒ₃はＨまたはベンゼン環を含んでも良い炭素数１〜２０のアルキル基を表す。） General formula (4)

(R ₁ represents H or CH ₃ , R ₂ represents an alkylene group, R ₃ represents H or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring.)

The compound (a) represented by the general formula (4) which is a constituent component of the transparent resin has good adsorption / orientation on the pigment surface due to the effect of π electrons of the benzene ring. In particular, when (a) is paracumylphenol ethylene oxide or propylene oxide modified (meth) acrylate, its steric effect is added and a better adsorption / orientation plane can be formed on the pigment, which is more effective. . Although the carbon number of the alkyl group of R ₃ is from 1 to 20, preferably 1 to 10. When the number of carbon atoms is from 1 to 10, the alkyl group becomes an obstacle to suppress the approach between the resins and promote the adsorption / orientation to the pigment. Even the adsorption / orientation to the pigment surface is hindered. This becomes more prominent as the chain length becomes longer, and when the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely lowered.

  Examples of the compound (a) include phenol ethylene oxide modified (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate and the like.

  As the compound (b), (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate, (iso) pentyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate acid phosphooxyethyl (meth) Examples thereof include acrylate, acid phosphooxypropyl (meth) acrylate, 3 chloro 2-acid phosphooxyethyl (meth) acrylate, and acid phosphooxypolyethylene glycol mono (meth) acrylate.

The proportion of the compound (a) in the compound constituting the transparent resin is preferably 0.1 to 50% by weight, more preferably 10 to 35% by weight. When the proportion of the compound (a) is less than 0.1% by weight, a sufficient pigment dispersion effect cannot be obtained, and when it is more than 50% by weight, the compatibility with other components in the coloring composition is lowered. In some cases, precipitation of the monomer or photopolymerization initiator may occur.
The weight average molecular weight (Mw) of the transparent resin is preferably 5,000 to 100,000, more preferably 10,000 to 50,000.

  As monomers and oligomers constituting the pigment carrier, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Various acrylic esters and methacrylic esters such as dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, (Meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, acrylonitrile and the like.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone photopolymerization initiators such as zoyl-4′-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -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 , 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and other triazine photopolymerization initiators, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators, etc. It is done.

  The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.

The colored composition of the present invention is produced by a method in which a pigment is dispersed in a pigment carrier solution, a method in which a pigment dispersion is prepared by dispersing a pigment in water or an organic solvent, and then mixed with the pigment carrier solution. . The method for dispersing the pigment is not particularly limited, but a method using a bead mill, a sand mill, a ball mill, a three roll mill, a two roll mill or the like is preferable. When a pigment derivative is used, the pigment and the pigment derivative can be separately dispersed in the pigment carrier solution and then mixed. However, in order to improve the dispersibility of the pigment, the pigment derivative is dispersed when the pigment is dispersed. Is preferably added.
When dispersing the pigment in the pigment carrier, a dispersion aid such as a surfactant can be appropriately used.

  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. , 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 Anionic surfactants such as: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as nylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactant; Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaines and alkylimidazolines. These can be used alone or in admixture of two or more.

  In order to make it easy to form a filter segment by applying the colored composition on a transparent substrate such as a glass substrate so as to have a dry film thickness of 1 to 2.5 μm, it can contain a solvent. . Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination.

  The coloring composition can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist material. The colored resist material is obtained by dispersing three kinds of pigments in a composition containing a thermosetting resin, a thermoplastic resin or a photosensitive resin, a monomer, and a photopolymerization initiator.

The three kinds of pigments are preferably contained in a ratio of 1.5 to 7% by weight in total when the filter segment is formed by a photolithographic method, and the filter segment is formed by a printing method. When it does, it contains in the ratio of 1.5 to 40 weight% in total in a coloring composition. In any case, the three pigments are preferably contained in the final filter segment in a proportion of 10 to 40% by weight, more preferably 20 to 40% by weight, with the remainder depending on the pigment carrier. It consists essentially of the resinous binder provided.
The coloring composition is used to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust by means of centrifugation, sintered filter, membrane filter or the like. Preferably it is done.

Next, the color filter will be described.
In the color filter of the present invention, three color filter segments of R (red), G (green), and B (blue) are formed on a transparent or reflective substrate. The green filter segment is formed by using the coloring composition of the present invention by a printing method or a photolithography method.

  The red filter segment can be formed using a normal red coloring composition. For example, CI Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 3, 48: 4, 81: 1, 81: 2, 81: instead of the three pigments. 3, 81: 4, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279, etc. It is a composition. An orange pigment such as C.I. Pigment Orange 43, 71, 73 can be used in combination with the red coloring composition.

  The blue filter segment can be formed using a normal blue coloring composition. For example, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. may be used instead of the three pigments. It is a composition obtained using a pigment. Purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 can be used in combination with the blue coloring composition.

As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is coated with silica, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
As the reflective substrate, silicon or a substrate in which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed on the transparent substrate is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. 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 each color filter segment by a photolithography method, the colored composition prepared as the solvent developing type or alkali developing type colored resist material is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a coating method, coating is performed 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 an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-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, or the like in addition to the above method, but the colored 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 transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there.
The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

  If a black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast ratio of the liquid crystal display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.
The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.
Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.

Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% and 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, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. Acrylic resin solution 1 was prepared.

(Preparation of acrylic resin solution 2)
In a reaction vessel similar to the preparation of acrylic resin solution 1, 800 parts of cyclohexanone is heated to 100 ° C. while injecting nitrogen gas into the container, and 60.0 parts of styrene and 60.0 parts of methacrylic acid are added from the dropping tube at the same temperature. A mixture of 65.0 parts of methyl methacrylate, 65.0 parts of methyl methacrylate, 10.0 parts of butyl methacrylate and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction.
After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain a weight average molecular weight. A solution of about 40,000 acrylic resin was obtained.
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, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. Acrylic resin solution 2 was prepared.

(Preparation of yellow treated pigment 1)
Isoindoline-based yellow pigment CI Pigment Yellow 185 (BASF “Paliogen Yellow D1155”): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) at 120 ° C. For 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow-treated pigment 1 were obtained.

(Preparation of yellow treated pigment 2)
Azo-based yellow pigment CI Pigment Yellow 150 (“E-4GN” manufactured by BAYER): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 4 ° C. at 4 ° C. Kneaded for hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow-treated pigment 2 were obtained.

(Preparation of green treated pigment 1)
A phthalocyanine-based green pigment CI Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho). The mixture was kneaded at 120 ° C. for 4 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of green-treated pigment 1 were obtained.

(Preparation of green treated pigment 2)
Phthalocyanine green pigment CI Pigment Green 7 (“Lionol Green YS-07” manufactured by Toyo Ink Mfg. Co., Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts on a stainless gallon kneader (manufactured by Inoue Seisakusho) Charged and kneaded at 120 ° C. for 4 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of green-treated pigment 1 were obtained.

[Examples 1-6, Comparative Examples 1-4]
After uniformly mixing a mixture of three pigments and dye derivatives of the blending amounts shown in Tables 11 and 12 with 50.0 parts of acrylic resin solution 1 and 40.0 parts of cyclohexanone, zirconia beads having a diameter of 1 mm Was dispersed with an Eiger mill for 3 hours and filtered through a 5 μm filter to prepare a pigment dispersion.

＊１：色素誘導体は、表１〜９に示す化合物を意味する。
＊２：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １３９はＣｉｂａ社製「イルガフォア
イエロー ２Ｒ−ＣＦ」

* 1: A pigment derivative means the compound shown in Tables 1-9.
* 2: C.I. I. Pigment Yellow 139 is made by Ciba "Irgafore Yellow 2R-CF"

Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain an alkali developing type green resist material.
Pigment dispersion shown in Table 11 or Table 60.0 parts Photopolymerization initiator (“Irgacure 907” manufactured by Ciba) 1.2 parts Trimethylolpropane triacrylate 4.2 parts (“Nakester” manufactured by Shin-Nakamura Chemical Co., Ltd.) ATMPT ")
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 1.4 parts Acrylic resin solution 2 11.0 parts Cyclohexanone 23.2 parts

  The obtained resist material was applied to a film thickness of x = 0.277 and y = 0.600 on a 100 mm × 100 mm, 1.3 mm thick glass substrate using a spin coater. Next, after drying at 70 ° C. for 20 minutes, ultraviolet exposure was performed with an integrated light amount of 150 mJ using an ultrahigh pressure mercury lamp. The coated substrate was heated at 230 ° C. for 1 hour and allowed to cool, and then the brightness (Y) of the obtained green coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optics) Asked. Moreover, the surface state of the coating film was observed with an optical microscope ("BX60" manufactured by Olympus Optical Co., Ltd.). The evaluation results are shown in Tables 13 and 14.

As shown in Table 13, since the green coating film formed using the colored composition (resist material) of Examples 1 to 3 contains two specific yellow pigments in the coating film, comparison is made. Compared with the green coating film formed using the colored composition (resist material) of Examples 1 and 2, it has a good transmission spectrum for the light source, and as a result, the brightness Y is high.

As shown in Table 14, since the green coating film formed using the coloring composition (resist material) of Examples 4 to 6 contains two specific yellow pigments in the coating film, comparison is made. Compared with the green coating film formed using the colored composition (resist material) of Examples 3 to 4, it has a good transmission spectrum for the light source, and as a result, the brightness Y is high.

Next, a red resist material and a blue resist material were prepared by the following method in order to evaluate white brightness, color temperature, and the like of the color filter including the red filter segment, the blue filter segment, and the green filter segment.
(Red resist material)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a red dispersion. An alkali-developable red resist material was obtained in the same manner as the green resist material except that a red pigment dispersion was used instead of the pigment dispersion shown in Table 11.
Red pigment ("Irgaphore Red B-CF" manufactured by Ciba) 9.0 parts Dye derivative A-52 shown in Table 9 1.0 part Acrylic resin solution 1 50.0 parts Cyclohexanone 40.0 parts

(Blue resist material)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a blue dispersion. An alkali-developable blue resist material was obtained in the same manner as the green resist material except that a blue pigment dispersion was used instead of the pigment dispersion shown in Table 11.
Blue pigment (Toyo Ink Manufacturing Co., Ltd. “Lionol Blue ES”) 9.0 parts Dye derivative A-47 shown in Table 8 1.0 part Acrylic resin solution 1 50.0 parts Cyclohexanone 40.0 parts

A red resist material was applied to a glass substrate by spin coating so as to have a chromaticity of x = 0.603 and y = 0.328 with a C light source. After drying, striped pattern exposure was performed with an exposure machine and development was performed with an alkaline developer for 90 seconds to form a striped red filter segment. The alkali developer is composed of 8.0% sodium carbonate 1.5% sodium hydrogen carbonate 0.5% anionic surfactant ("Perrex NBL" manufactured by Kao Corporation) and 90% water.
Next, the green resist materials obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were coated with a C light source so as to have a chromaticity of x = 0.277 and y = 0.600. After drying, a striped pattern adjacent to the red filter segment was exposed with an exposure machine to form a striped green filter segment.
Further, a blue resist material is applied with a film thickness such that x = 0.136 and y = 0.142 with a C light source, and a striped blue filter segment adjacent to a red filter segment and a green filter segment. Formed.

The shape of each color filter segment was good, and the resolution was also good. Finally, the obtained color filter is heated in an oven at 230 ° C. for 30 minutes to completely react with the remaining polymerizable functional groups, and a red, green, and blue stripe-shaped stripe shape is formed on the transparent substrate. A color filter comprising filter segments was obtained.
The brightness Y of each color of the obtained color filter with a C light source was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). In addition, when light is transmitted through all three colors, white light is obtained. The x, y, Y, color temperature K, duv of the white light was calculated from x, y, Y of each color. The results are shown in Tables 15 and 16.

As shown in Table 15, the white brightness Y of the color filter including the green filter segment formed using the green resist material obtained in Examples 1 to 3 has substantially the same color temperature K and duv value. Nevertheless, the color filter is higher than that using the green resist material obtained in Comparative Example 1 and Comparative Example 2 and white is bright.

As shown in Table 16, the whiteness Y of the color filter having the green filter segment formed using the green resist material obtained in Examples 4 to 6 has substantially the same color temperature K and duv value. However, the color filter is higher than that using the green resist material obtained in Comparative Example 3 and Comparative Example 4 and white is bright.

Claims (5)

A pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, an isoindoline pigment represented by the following general formula (1), and an azo pigment represented by the following general formula (2) in a weight ratio: A coloring composition for a color filter, comprising a ratio of 34.7: 65.3 to 98.3: 1.7 and further containing a phthalocyanine pigment represented by the following general formula (3):
General formula (1)

[R ₁ and R ₂ each independently represents CN or CONHCH ₃ . ]
General formula (2)

[Y represents Cu, K, Ca, Na, Ni, Fe, Al, Co, or S. ]
General formula (3)

[X _{1 to} X ₁₆ each independently represent H, F, Cl, Br, or I. Z represents Cu, K, Ca, Ni, Fe, Al, Co, or S. ]
  The coloring composition for a color filter according to claim 1, comprising a pigment derivative having a basic group or a triazine derivative having a basic group.   The coloring composition for a color filter according to claim 1 or 2, wherein the isoindoline pigment is C.I. Pigment Yellow 185, the azo pigment is C.I. Pigment Yellow 150, and the phthalocyanine pigment is C.I. Pigment Green 36 or C.I. Pigment Green 7. The pigment carrier contains a transparent resin obtained by copolymerizing the compound (a) represented by the following general formula (4) and another compound (b) having an ethylenically unsaturated double bond. The coloring composition for color filters according to any one of claims 1 to 3.
General formula (4)

(R ₁ represents H or CH ₃ , R ₂ represents an alkylene group, R ₃ represents H or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring.)   5. Comprising at least one red filter segment, at least one blue filter segment, and at least one green filter segment, wherein the at least one green filter segment is formed from the colored composition according to claim 1. A color filter characterized by having