JP4649291B2 - COLORING COMPOSITION MANUFACTURING METHOD AND COLOR FILTER USING COLORED COMPOSITION PRODUCED BY THE METHOD - Google Patents

Description

  The present invention relates to a method for producing a colored composition suitably used for producing a color filter used for a color liquid crystal display device, a color imaging device, and the like, and a color filter using the colored composition produced by the method. It is.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. 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. There is an increasing demand for contrast.

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 in a fixed arrangement. It is made up of arranged ones. 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.
Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, 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.

However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.
Until now, in order to realize high brightness and high contrast of the color filter, the pigment contained in the filter segment has been refined.

However, the pigment is composed of a mixture of primary particles and secondary particles that are aggregates thereof, and generally the transparency improves as the degree of dispersion of the pigment is increased. In parallel with the progress of the dispersion from the secondary particles to the primary particles, the primary particles are crushed, which contributes to the increase in viscosity beyond the improvement of quality.
In other words, various refinements of pigments (similarly called crudes with a particle size of 10 to 100 μm, produced by chemical reaction, which are made into a mixture of primary particles and aggregated secondary particles by pigmentation) Even if the particles are refined by the treatment method, the pigments whose primary particles or secondary particles have been refined are generally easily aggregated, and when the refinement is excessively advanced, a huge lump of pigment solid is formed. Furthermore, even if the finely-divided pigment is dispersed in a pigment carrier containing a resin or the like and the secondary particles of the pigment are stabilized as close as possible to the primary particles, a stable coloring composition is obtained. It is very difficult.

  In addition, coloring compositions in which pigments that have been made finer are dispersed in a pigment carrier often show thixotropic properties due to the generation of coarse particles due to aggregation of pigment particles and the increase in viscosity over time. Such an increase in viscosity and poor fluidity of the colored composition causes various problems in production work and product value. For example, the filter segment of a color filter is generally formed by spin-coating a colored composition in which a pigment is dispersed in a pigment carrier containing a monomer and a resin on a glass substrate. If a poor coloring composition is used, a coating film having a uniform film thickness cannot be obtained due to poor spin coatability or poor leveling.

In order to solve the above problems, a pigment derivative having an organic pigment or the like as a base skeleton and an acidic or basic substituent in the side chain is mixed as a dispersant, and the pigment derivative and the resin component in the pigment carrier are mixed. There is known a method of stabilizing the dispersion of the pigment by the interaction. (For example, see Patent Documents 1 and 2.)
However, since the pigment derivative used as a dispersant is used in the form of a powder obtained by pulverizing a dry solid, and the pulverized particle size is as coarse as about 100 to 150 mesh pass, when the pigment is dispersed on the pigment carrier, There is a drawback that it does not work more effectively.
In addition, undispersed pigments and dye derivatives may contribute to filter segment defects.
JP 2001-51112 A JP 2004-204103 A

The first object of the present invention is to provide a method for producing a stable coloring composition having no coarse particles and excellent viscosity characteristics by effectively acting a pigment derivative used as a dispersant when dispersing a pigment on a pigment carrier. Is to provide.
A second object of the present invention is to provide a color filter having a uniform film thickness, few filter segment defects, and a high contrast ratio.

The method for producing a colored composition of the present invention disperses a dry pigment and removes water in a pigment carrier and an organic solvent comprising a transparent resin, a precursor thereof, or a mixture thereof in the presence of a water presscake of a pigment derivative. It is characterized by that. In the method for producing a colored composition of the present invention, the pigment carrier preferably contains a transparent thermoplastic resin. Further, the content of the dye derivative in the water presscake of the dye derivative is preferably 8 to 80% by weight based on the weight of the water presscake of the dye derivative. It is preferable that the weight of the pigment derivative in the water press cake is 0.001 to 40 parts by weight with respect to 100 parts by weight.
Moreover, the color filter of this invention is equipped with the filter segment formed from the coloring composition manufactured by the method of this invention on the board | substrate.

In the method for producing a coloring composition of the present invention, when a dry pigment is dispersed in a transparent resin, a pigment carrier made of a precursor thereof or a mixture thereof, and an organic solvent, a water presscake of a dye derivative having no dry aggregation as a dispersant. Is used. Therefore, it is possible to produce a colored composition in which the pigment derivative can be effectively acted from the initial stage of dispersion, dispersion can be advanced in a short time, and there are no coarse particles and no increase in viscosity due to overdispersion.
By forming a filter segment using the colored composition produced by the method of the present invention, a color filter having a uniform film thickness, a small amount of foreign matters caused by coarse pigment particles and pigment derivatives, and a high brightness and contrast ratio Is obtained.

First, a preferred embodiment will be given and the method for producing the colored composition of the present invention will be described in detail.
In the method for producing a colored composition of the present invention, a dry pigment is dispersed in a pigment carrier composed of a transparent resin, a precursor thereof or a mixture thereof and an organic solvent in the presence of a water presscake of a dye derivative.
The dry pigment is prepared by kneading a dry pigment, a pigment carrier, an organic solvent, and a water presscake of the dye derivative, and separating and removing the water contained in the water presscake of the pigment dispersion and the dye derivative. It can be dispersed in a pigment carrier and an organic solvent in the presence of a water presscake.

  The water presscake of a pigment derivative used in the method for producing a colored composition of the present invention is obtained by subjecting a suspension of a pigment derivative produced in an aqueous system to a method such as filter press, centrifugation, ultrafiltration, and vacuum filtration. Reduced water content. The content of the pigment derivative in the water presscake of the pigment derivative is preferably 8 to 80% by weight, more preferably 20 to 60% by weight, based on the weight of the water presscake of the pigment derivative (100% by weight). is there. When the pigment derivative content in the water press cake of the pigment derivative is lower than 8% by weight, water is separated, and the uniformity of the pigment derivative in the water press cake becomes insufficient. In addition, when the content of the dye derivative in the water presscake of the dye derivative is higher than 80% by weight, the water presscake of the dye derivative becomes hard and the mixing property with the pigment and the pigment carrier is inferior. The effect of can not be fully demonstrated.

The pigment derivative is a compound represented by the following general formula (1), and there are those having a basic substituent and those having an acidic substituent.
General formula (1)
AB
A: Organic dye residue B: Basic substituent or acidic substituent

  In the general formula (1), examples of the organic dye constituting the organic dye residue of A include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthra Anthraquinone dyes such as pyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone dye, dioxazine dye, perinone dye, perylene dye, thioindigo dye, isoindosulfone dye, isoindolinone dye Examples thereof include dyes, quinophthalone dyes, selenium dyes, and metal complex dyes. The organic dye constituting the organic dye residue includes light-colored anthraquinone, acridone, and triazine. Moreover, the pigment illustrated later may be sufficient.

Anthraquinone and acridone constituting the organic dye residue are an alkyl group such as a methyl group or an ethyl group, an amino group, a nitro group, a hydroxyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a substituent such as a halogen such as chlorine. You may have.
The triazine constituting the organic dye residue is an alkyl group such as a methyl group or an ethyl group, an amino group or a dimethylamino group, an alkylamino group such as a diethylamino group or a dibutylamino group, a nitro group, a hydroxyl group, or a methoxy group, It may have a substituent such as an alkoxy group such as an ethoxy group or a butoxy group, a halogen such as chlorine, a phenyl group or a phenylamino group. Further, the phenyl group and the phenylamino group may be substituted with a methyl group, an ethyl group, a methoxy group, an ethoxy group, an amino group, a dimethylamino group, a diethylamino group, a nitro group, a hydroxyl group, or the like.

一般式（３）

In the general formula (1), examples of the basic substituent of B include substituents represented by the following general formulas (2), (3), (4), and (5).
General formula (2)

General formula (3)

一般式（５）

General formula (4)

General formula (5)

In the general formulas (2) to (5), each symbol is as follows.
X represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10. n is preferably 1 to 3.
R ₁ and R ₂ each independently represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted phenyl group, or R ₁ and R ₂ are bonded to each other to form nitrogen, oxygen Alternatively, it represents an unsubstituted or substituted heterocycle containing a sulfur atom. Unsubstituted or substituted alkyl groups represented by R ₁ or R ₂ usually have 1 to 36 carbon atoms. Also, the unsubstituted or substituted alkenyl group represented by R ₁ or R ₂ usually has 2 to 36 carbon atoms. R ₁ and R ₂ are each preferably an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms.

R ₃ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted phenyl group. Unsubstituted or substituted alkyl group represented by R ₃ typically have from 1 to 36 carbon atoms. Also, the unsubstituted or substituted alkenyl group represented by R ₃ usually has 2 to 36 carbon atoms. R ₃ is preferably an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms.
R ₄ , R ₅ , R ₆ , and R ₇ each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted phenyl group. Unsubstituted or substituted alkyl groups represented by R ₄ , R ₅ , R ₆ , or R ₇ typically have 1 to 36 carbon atoms. Also, the unsubstituted or substituted alkenyl group represented by R ₄ , R ₅ , R ₆ , or R ₇ typically has 2 to 36 carbon atoms. R ₄ , R ₅ , R ₆ , or R ₇ are each preferably an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms.

Y represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted phenyl group. Unsubstituted or substituted alkyl groups represented by R ₈ or R ₉ usually have 1 to 36 carbon atoms. Also, the unsubstituted or substituted alkenyl group represented by R ₈ or R ₉ usually has 2 to 36 carbon atoms. R ₈ and R ₉ are each preferably a hydrogen atom.
Z represents an unsubstituted or substituted alkylene group, an unsubstituted or substituted alkenylene group, or an unsubstituted or substituted phenylene group. Unsubstituted or substituted alkylene groups represented by Z usually have 1 to 36 carbon atoms. Also, the unsubstituted or substituted alkenylene group represented by Z usually has 2 to 36 carbon atoms. Z is preferably an unsubstituted or substituted phenylene group.

一般式（７）

一般式（６）および（７）において、Ｒ₁〜Ｒ₇、およびｎは、一般式（２）〜（４）に関して定義したとおりである。 P represents a substituent represented by the following general formula (6) or a substituent represented by the following general formula (7).
Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the following general formula (6), or a substituent represented by the following general formula (7). Q is preferably a substituent represented by the following general formula (6).
General formula (6)

General formula (7)

In the general formulas (6) and (7), R _{1 to} R ₇ and n are as defined for the general formulas (2) to (4).

一般式（９）

Moreover, as an acidic substituent, the substituent represented by the following general formula (8) and (9) is mentioned.
General formula (8)

General formula (9)

In the general formulas (8) and (9), each symbol is as follows.
M represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom or an aluminum atom.
i represents the valence of M.
R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ are each independently a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted phenyl group, or a poly having an alkyl group at the end. Represents an oxyalkylene group. The unsubstituted or substituted alkyl group represented by R ₁₀ , R ₁₁ , R ₁₂ , or R ₁₃ usually has 1 to 36 carbon atoms. Also, the unsubstituted or substituted alkenyl group represented by R ₁₀ , R ₁₁ , R ₁₂ , or R ₁₃ typically has 2 to 36 carbon atoms.
Also, the polyoxyalkylene group represented by R ₁₀ , R ₁₁ , R ₁₂ , or R ₁₃ usually has 2 to 5 carbon atoms. Examples of the polyoxyalkylene group include a polyoxyethylene group and a polyoxypropylene group.
R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ are each preferably a hydrogen atom, a methyl group, an octyl group, a dodecyl group, and a stearyl group.

  Examples of the amine component used for forming the substituents represented by the general formulas (2) to (7) 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 N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylamino Amylamine, 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-laurylamino The Pyramine, 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 Examples thereof include propylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

The amine component used to form the sulfonic acid amine salt of formula (9) may be any primary, secondary, tertiary or quaternary amine.
Examples of primary amines include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine , Nonadecylamine, amine such as eocosylamine, or unsaturated amine corresponding to the number of carbon atoms. The amine and unsaturated amine may have a side chain.

Examples of secondary amines include dioleylamine and distearylamine.
Examples of the tertiary amine include dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmethylamine, and trioctylamine.
Examples of the quaternary amine include dimethyl didodecyl ammonium chloride, dimethyl dioleyl ammonium chloride, dimethyl didecyl ammonium chloride, dimethyl dioctyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl decyl ammonium chloride, trimethyl hexadecyl. Ammonium chloride, trimethyloctadecylammonium chloride, dimethyldodecyltetradecylammonium chloride, dimethylhexadecyloctadecylammonium chloride, etc. are mentioned.

Specific examples of the dye derivative are shown below with compound numbers, but are not limited thereto. These pigment derivatives can be used alone or in admixture of two or more.

  The amount of the dye derivative used in dispersing the pigment in the pigment carrier in the presence of the dye derivative water press cake is preferably the weight of the dye derivative in the water press cake of the dye derivative with respect to 100 parts by weight of the pigment. The amount is 0.001 to 40 parts by weight, more preferably 1 to 20 parts by weight. When the usage-amount of a pigment derivative is less than 0.001 weight part and exceeds 40 weight part, the viscosity of the coloring composition obtained will become high, thixotropy will express, and coating suitability will become low.

The dry pigment used in the method for producing a colored composition of the present invention is an organic or inorganic pigment having a non-volatile content of approximately 93% by weight or more, and one kind of pigment is used alone or two or more kinds of pigments are mixed. Can be used. By using a dry pigment, the pigment, pigment carrier, organic solvent, and dye derivative water presscake are kneaded as compared with the case of using a pigment water presscake, and when performing pigment dispersion and water separation and removal, The amount of water from the water press cake is small, and water can be easily separated and removed. Further, since the change in viscosity before and after separation and removal is small, the dispersion is much better than in the case of using a water press cake of pigment.
The pigment is preferably a pigment having a high color developability and a high heat resistance, particularly a pigment having a high heat decomposition resistance, and an organic pigment is usually used.
Below, the specific example of the organic pigment which can be used for the manufacturing method of the coloring composition of this invention is shown with a color index number.

  Red pigmented compositions for forming red filter segments include, for example, CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2. 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224 Red pigments such as 226, 227, 228, 240, 246, 254, 255, 264, and 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red coloring composition.

  Examples of the yellow coloring composition for forming the yellow filter segment include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20. 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc. be able to.

For example, an orange pigment such as CI Pigment orange 36, 43, 51, 55, 59, 61 can be used as the orange coloring composition for forming the orange filter segment.
As the green coloring composition for forming the green filter segment, for example, a green pigment such as CI Pigment Green 7, 10, 36, 37 can be used. A yellow pigment can be used in combination with the green coloring composition.
Examples of blue coloring compositions for forming blue filter segments include CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. Blue pigments can be used. Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination with the blue coloring composition.

For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 or the like is used as a cyan coloring composition for forming a cyan filter segment. Can do.
For the magenta coloring composition for forming the magenta color filter segment, for example, purple pigments and red pigments such as CI Pigment Violet 1, 19, CI Pigment Red 144, 146, 177, 169, 81 can be used. A yellow pigment can be used in combination with the magenta colored composition.

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber , Titanium black, synthetic iron black, carbon black and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
When the coloring composition is produced, a dye can be used in combination within the range in which the heat resistance is not lowered for color matching.

  The pigment is preferably contained in the coloring composition at a ratio of 1.5 to 25% by weight. Further, the pigment is preferably contained in the final filter segment in a proportion of 10 to 40% by weight, more preferably 20 to 40% by weight, and the remainder substantially consists of a resinous binder provided by the pigment carrier. .

The pigment carrier used in the method for producing the colored composition of the present invention is composed of a transparent resin, a precursor thereof, or a mixture thereof.
Monomers that are precursors of transparent resins include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxy. Ethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate , Neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate, etc. Various acrylic esters and methacrylic esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- Examples thereof include vinylformamide and acrylonitrile, and these can be used alone or in admixture of two or more.

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 these can be used alone or in combination of two or more. The pigment carrier is kneaded with the water press cake of the pigment, organic solvent and dye derivative, and separated and removed from the water press cake of the dye derivative together with the pigment dispersion. It is preferable to include a thermoplastic resin.
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. , Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polypropylene, polybutadiene, 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.

  As the photosensitive resin, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or 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 cinnamic acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. In addition, 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 organic solvent used in the method for producing the colored composition of the present invention is applied in such a manner that the pigment is sufficiently dispersed in the pigment carrier and the dry film thickness is 0.2 to 5 μm on a transparent substrate such as a glass substrate. This is a component for facilitating the formation of the filter segment. Examples of the organic 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, and petroleum solvents. A solvent can be used individually by 1 type or in combination of 2 or more types.
The solvent is usually used in an amount of 50 to 5000 parts by weight, preferably 100 to 2500 parts by weight, based on 100 parts by weight of the pigment.

When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the colored composition produced by the method of the present invention.
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-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (to Chloromethyl) -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 and the like are used. It is done.
The photopolymerization initiator can be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of the pigment.

These photopolymerization initiators are used alone or in admixture of two or more. As sensitizers, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanth Such as lenquinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. A compound can also be used in combination.
The sensitizer can be used in an amount of 0.1 to 100 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

The coloring composition can be adjusted in the form of a solvent development type or alkali development type colored resist material. The colored resist material is prepared by using various dispersing means in a pigment carrier containing a thermoplastic resin, a thermosetting resin or a photosensitive resin and a monomer and an organic solvent in the presence of a water derivative of a pigment derivative. It is dispersed. The coloring composition can also be produced by mixing several pigments separately dispersed in a pigment carrier and an organic solvent in the presence of a water presscake of a pigment derivative.
The colored composition is removed by means of centrifugal separation, sintering filter, membrane filter, etc. to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles It is preferable to carry out.

When dispersing the pigment in the pigment carrier and the organic solvent, a dispersion aid such as a resin-type pigment dispersant or a surfactant can be appropriately used. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in the pigment carrier using the dispersion aid is used. Provides a color filter excellent in transparency.
These dispersing aids may be used alone or in combination of two or more. Such a dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the pigment.

  The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and acts to stabilize the dispersion of the pigment on the pigment carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment 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 alkylamines. Salts, polysiloxanes, long-chain polyaminoamide sulfonates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) with polyesters having free carboxyl groups, and the like Salt or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are used. These can be used alone or in admixture of two or more.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazosulfone These may be used alone or in admixture of two or more.

  In addition, the coloring composition may contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. A phosphine, a sulfonate, etc. are mentioned.

The color filter of the present invention comprises a filter segment formed on a substrate from the colored composition produced by the method of the present invention.
The color filters include at least one red filter segment, at least one green filter segment, and at least one blue filter segment, at least one magenta filter segment, at least one cyan filter segment, and at least One having one yellow color filter segment may be mentioned.

The color filter of this invention can be manufactured by forming the filter segment of each color on a board | substrate using the coloring composition manufactured by the method of this invention by the photolithographic method or the printing method.
As the substrate, a glass plate having a high transmittance with respect to visible light, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate 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 various printing inks, so the color filter manufacturing method is low cost and excellent in mass productivity. Yes. 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 is not dried and solidified 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.

  The formation of each color filter segment by photolithography is performed by the following method. That is, the coloring composition prepared as the solvent developing type or alkali developing type colored resist material is applied on the substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. Apply 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 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. 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 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.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.
First, preparation of acrylic resin solutions used in Examples and Comparative Examples, and methods for evaluating pigment dispersions and resist materials will be described.

(Preparation of acrylic resin solution)
430 parts of methoxypropyl acetate is placed in a reaction vessel, heated to 100 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 60.0 parts of styrene, 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, methacrylic acid A mixture of 65.0 parts of butyl acid and 10.0 parts of azobisbutyronitrile was added dropwise over 1 hour to carry out polymerization. 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 methoxypropyl acetate was added, and the reaction was continued for another 1 hour. Obtained. The weight average molecular weight of the acrylic resin was about 40,000 (measured by GPC). After the obtained acrylic resin solution was cooled to room temperature, a part of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, so that the nonvolatile content was 35% by weight. Methoxypropyl acetate was added to the obtained resin solution to prepare a pigment dispersion and an acrylic resin solution used for resist formation.

(Evaluation methods)
The viscosity of the pigment dispersion was measured using a B-type viscometer (BL type manufactured by Toki Sangyo Co., Ltd.). The viscosity at 2 rotors, 6 rpm, 25 ° C. was measured. Further, a viscosity ratio between 6 rpm and 60 rpm (referred to as a thixo index, the larger the value, the higher the thixotropic property) was obtained, and the thixotropic property was evaluated.
The viscosity of the resist material was measured using an E-type viscometer (TV20 type, manufactured by Toki Sangyo Co., Ltd.) at 1 ° 34 ′ × R24 cone, 20 rpm, and 25 ° C. The viscosity ratio of 6 rpm and 60 rpm was determined in the same manner as described above.

Next, a method for measuring the contrast ratio of a coating film prepared using a resist material will be described. The contrast ratio was measured using the measuring apparatus shown in FIG. The light emitted from the backlight unit for liquid crystal display (7) passes through the polarizing plate (6), is polarized, passes through the dry coating film (4) of the resist material applied on the glass substrate (5), It reaches the polarizing plate (3). If the polarization planes of the polarizing plate (6) and the polarizing plate (3) are parallel, light is transmitted through the polarizing plate (3), but if the polarization plane is perpendicular, the light is transmitted by the polarizing plate (3). Blocked. However, when the light polarized by the polarizing plate (6) passes through the dry coating film (4) of the resist material, scattering due to pigment particles occurs, and if a part of the polarization plane is displaced, the polarizing plate When parallel, the amount of light transmitted through the polarizing plate (3) is reduced, and when the deflecting plate is perpendicular, part of the light is transmitted through the polarizing plate (3). This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)

Therefore, when scattering occurs due to the pigment of the dry coating film (4) of the resist material, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered.
A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter (1), and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask (2) having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.
The number of particles (2 μm or more) of the pigment dispersion coating film is a binary value of 450 × 4 images (1 field: 200 × 200 μm) using a microscope (“Digital HF Microscope VH8000” manufactured by Keyence Corporation). And the number of particles of 2 μm or more was measured.
In addition, the contrast ratio of the resist material coating film and the coating film for measuring the number of particles of the pigment dispersion coating film are dried on a 100 × 100 × 0.7 mm glass substrate which has been washed and dried, and the pigment dispersion and resist material are dried using a spin coater. The film was applied to a thickness of 1.5 μm and dried at 80 ° C. for 30 minutes.

[Example 1]
49.9 parts of blue pigment ("Lionol Blue ES", CI Pigment Blue 15: 6, manufactured by Toyo Ink Mfg. Co., Ltd.) and Compound 1 (pigment) with respect to 100 parts of an acrylic resin solution having a nonvolatile content of 35% by weight Derivative) water press cake (pigment derivative content 45% by weight) 5.9 parts was kneaded for 30 minutes with a desktop kneader ("PNV-1 type" manufactured by Irie Shokai Co., Ltd.). At this time, the separated water was removed with a condenser and then diluted with 190 parts of methoxypropyl acetate. Further, this mixture was dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm for 3 hours, adjusted to a non-volatile content of 20% by weight with methoxypropyl acetate, and 5 μm Filtration through a filter gave a blue pigment dispersion.
Next, 30 parts of the obtained blue pigment dispersion, 12 parts of an acrylic resin solution having a nonvolatile content of 35% by weight, 5.6 parts of a monomer, 2.0 parts of a photopolymerization initiator, 0.2 part of a sensitizer, methoxypropyl acetate After stirring and mixing so that 50.2 parts were uniform, the mixture was filtered through a 2 μm filter, and further filtered through a 0.6 μm filter to obtain an alkali developing blue resist material.
The monomer is trimethylolpropane triacrylate (“NK ESTER ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), the photopolymerization initiator is “Irgacure 907” (manufactured by Ciba Geigy), and the sensitizer is “EAB-F”. (Hodogaya Chemical Co., Ltd.) was used.

[Example 2]
Except for changing the pigment derivative content in the water press cake of Compound 1 (pigment derivative) used in Example 1 to 20% by weight and changing the amount used to 13.4 parts, the same procedure as in Example 1 was performed. A blue pigment dispersion was obtained. Next, a blue resist was obtained in the same manner as in Example 1.

[Example 3]
Except for changing the pigment derivative content in the water press cake of Compound 1 (pigment derivative) used in Example 1 to 55% by weight and changing the usage amount to 4.8 parts, the same procedure as in Example 1 was performed. A blue pigment dispersion was obtained. Next, a blue resist was obtained in the same manner as in Example 1.

[Example 4]
A water press cake of 49.9 parts of a red pigment (“Chromophthal Red A2B”, CI Pigment RED177 manufactured by Ciba Geigy Co., Ltd.) and Compound 10 (pigment derivative) with respect to 100 parts of an acrylic resin solution having a nonvolatile content of 35% by weight ( 13.1 parts of pigment derivative content (40% by weight) were kneaded for 30 minutes with a table type kneader ("PNV-1 type" manufactured by Irie Shokai Co., Ltd.). At this time, the separated water was discharged by turning over the kneader, and then diluted with 190 parts of methoxypropyl acetate. Further, this mixture was dispersed with Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 4 hours using zirconia beads having a diameter of 1 mm, adjusted to a non-volatile content of 20% by weight with methoxypropyl acetate, 5 μm Filtration through a filter gave a red pigment dispersion.
Next, 30 parts of the obtained red pigment dispersion, 12 parts of an acrylic resin solution having a nonvolatile content of 35% by weight, 5.6 parts of a monomer, 2.0 parts of a photopolymerization initiator, 0.2 part of a sensitizer, methoxypropyl acetate After stirring and mixing 50.2 parts uniformly, the mixture was filtered through a 2 μm filter, and further filtered through a 0.6 μm filter to obtain an alkali developing red resist.
The monomer is trimethylolpropane triacrylate (“NK ESTER ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), the photopolymerization initiator is “Irgacure 907” (manufactured by Ciba Geigy), and the sensitizer is “EAB-F”. (Hodogaya Chemical Co., Ltd.) was used.

[Comparative Example 1]
A blue pigment dispersion was prepared in the same manner as in Example 1 except that 5.9 parts of the water presscake of Compound 1 (pigment derivative) used in Example 1 was changed to 2.6 parts of Compound 1 (pigment derivative) powder. Got. Next, a blue resist was obtained in the same manner as in Example 1.
[Comparative Example 2]
A red pigment dispersion was obtained in the same manner as in Example 4 except that 13.1 parts of the water press cake of compound 10 (dye derivative) used in Example 4 was changed to 5.3 parts of compound 10 (dye derivative) powder. Got. Subsequently, a red resist was obtained in the same manner as in Example 4.

For the pigment dispersions and resist materials obtained in Examples and Comparative Examples, the viscosity, the contrast ratio of the coating film, and the number of particles were evaluated. For the pigment dispersion, the viscosity after 7 days at 40 ° C. (accelerated aging) was also confirmed for the purpose of comparison of stability.
The results are shown in Table 1.

It is a conceptual diagram of the measuring apparatus for measuring a contrast ratio.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Luminometer 2 Mask 3 Polarizing plate 4 Colored composition dry coating film 5 Glass substrate 6 Polarizing plate 7 Backlight unit

Claims (4)

  A method for producing a coloring composition comprising dispersing a dry pigment in a transparent resin, a precursor thereof or a mixture thereof and an organic solvent and removing water in the presence of a water press cake of the dye derivative, The coloring composition content in the water presscake of a derivative is 8 to 80 weight% on the basis of the weight of the water presscake of a pigment derivative, The manufacturing method of the coloring composition characterized by the above-mentioned.   The method for producing a colored composition according to claim 1, wherein the pigment carrier contains a transparent thermoplastic resin.   The amount of the dye derivative used in the water presscake is an amount such that the weight of the dye derivative in the water presscake is 0.001 to 40 parts by weight with respect to 100 parts by weight of the pigment. The manufacturing method of the coloring composition of 2. A colored composition produced by the method according to any one of claims 1 to 3.

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