JP2007155782A - Method for producing colored composition, colored composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a colored composition having good fluidity, good wetting property to a filter and good filtering property. <P>SOLUTION: A method for producing a colored composition is provided in which a pigment dispersion obtained by mixing and dispersing a pigment, a pigment derivative and a pigment carrier (A) comprising a transparent resin, its precursor or a mixture of those is subjected to ultrasonic treatment, mixed with a pigment carrier (B) and filtered. The colored composition is obtained by the method. A color filter with filter segments formed using the colored composition is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a colored composition, a colored composition, and a color filter.

  The color filter has a configuration in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or the fine filter segments are arranged in a fixed arrangement. It consists of an arranged configuration. 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.

  In general, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is generally necessary to form them at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, the color filter manufacturing method mainly uses a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant.

  Color filters are generally composed of fine pixel patterns colored in the three primary colors of light, red, green, and blue, in a fixed arrangement, and various manufacturing methods have been proposed. Has been. In this method, a photosensitive composition in which a pigment called a pigment resist is transparently dispersed is uniformly applied to a glass substrate, the solvent is removed, and then exposed to ultraviolet rays through a photomask having a pixel pattern formed thereon. A pixel is formed by washing the unexposed portion with an alkaline aqueous solution. A color filter is produced by repeating this process for three colors of red, green, and blue.

  As another method, a dispersion of a pigment in an alkali-soluble binder resin solution is applied and dried, then a positive resist is applied, the pixel pattern is exposed to ultraviolet light, and this positive resist is used as an etching resist. There is a method of obtaining a pixel pattern of a color filter by developing with (this method is called “etching method”).

  Both the pigment resist method and the etching method are generally called a photolithography method (hereinafter referred to as “photolitho method”) because exposure and development are performed through a photomask. In the photolithography method, it is possible to use a solvent as a developing solution, but an alkaline aqueous solution is generally used in view of safety and environmental problems.

  In recent years, there has been a growing demand for color characteristics for color filters such as transmittance, that is, brightness and color purity, coating uniformity when forming pixels, sensitivity, developability, and pattern shape. In particular, color filters for solid-state imaging devices used in video cameras, digital cameras, color scanners, and the like are required to have high definition, high brightness, and high color reproducibility. In particular, regarding high definition, when a foreign matter of several microns is mixed in the filter segment, an incorrect signal is sent to the image sensor, causing a defect. The cause of foreign matters is mainly pigment secondary particles. So far, the dispersion of the pigment has been increased to reduce secondary particles, and further filtering through a filter with an appropriate pore size prevents contamination by foreign matters. did it.

  However, when the dispersion is excessive, there is a problem that the primary particles are crushed and reaggregation occurs in parallel with the dispersion of the pigment from the secondary particles to the primary particles. In addition, 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 may be formed. Furthermore, it has been very difficult to stabilize a pigment that has been further miniaturized by dispersing it in a pigment carrier containing a resin or the like and bringing the secondary particles closer to the primary particles.

  In addition, a colored composition in which a finely-divided pigment is dispersed in a pigment carrier often exhibits thixotropic properties due to generation of coarse particles and increase in viscosity due to aggregation of pigment particles 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, poor fluidity deteriorates the wettability with respect to the filter and causes a slow filtration rate.

  A technique for improving fluidity by applying shearing force and / or ultrasonic waves in an ink supply path of a colored composition has been disclosed so far from the viewpoint of improving the dischargeability of an inkjet head (Patent Document 1). The problem of foreign matter contamination and filtration characteristics in the filter segment, which is important for patterning, could not be solved.

JP 2002-277622 A

    An object of the present invention is to reduce pigment aggregation with the passage of time in a pigment dispersion, thereby reducing the kinematic viscosity by bringing the dispersion state of the pigment closer to the state immediately after the production of the pigment dispersion.

  According to the first aspect of the present invention, a pigment dispersion obtained by mixing and dispersing a pigment, a pigment derivative, and a pigment carrier (A) composed of a transparent resin, a precursor thereof, or a mixture thereof is ultrasonicated. After the treatment, the coloring composition is mixed with the pigment carrier (B) and filtered.

  A second invention is a method for producing a colored composition according to the first invention, wherein the pigment dispersion is repeatedly subjected to ultrasonic treatment by circulating through a closed channel.

  According to a third aspect of the present invention, there is provided a pipe that flows from a pigment dispersion tank to a raw material tank for other components used in the production of a colored composition, and an ultrasonic generator is provided in the middle of the inflow path, The method for producing a colored composition according to the first or second invention, wherein the body is subjected to ultrasonic treatment when flowing into the raw material tank.

  A fourth invention is a colored composition obtained by the production method according to any one of the first to third inventions.

  5th invention is a color filter characterized by including the filter segment formed using the coloring composition as described in 4th invention.

  The method for producing a colored composition of the present invention comprises a pigment dispersion obtained by mixing and dispersing a pigment, a pigment derivative, and a pigment carrier (A) composed of a transparent resin, a precursor thereof or a mixture thereof. After ultrasonic treatment, the pigment is mixed with the pigment carrier (B) and filtered, so that a colored composition can be produced using a pigment dispersion having good pigment dispersion and low viscosity.

  In the method for producing a colored composition according to the present invention, since the ultrasonic dispersion is repeatedly performed by circulating through the flow path in which the pigment dispersion is closed, a colored composition with further advanced pigment dispersion can be obtained.

  The method for producing a colored composition of the present invention is provided with a pipe that flows from a pigment dispersion tank to a raw material tank for other components used in the production of the colored composition, and an ultrasonic generator is provided in the middle of the inflow path. Since the ultrasonic dispersion is performed when the pigment dispersion flows into the raw material tank, the ultrasonic treatment process can be incorporated into the manufacturing process, and the working efficiency is good.

  Since the colored composition of the present invention is obtained by the above production method, the fluidity is good. Moreover, the wettability with respect to a filter is favorable and the filtration speed is quick.

  The color filter of the present invention comprising a filter segment formed using the above colored composition has a good quality.

  The manufacturing method of the coloring composition of this invention is demonstrated in detail.

<Pigment derivative>
The pigment derivative used in the present invention 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, and anthrapyrimidine. , Flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone and other anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindosulfone dyes, isoindolinone dyes Quinophthalone dyes, selenium dyes, metal complex dyes, and the like. These organic dyes include light-colored anthraquinones, acridones, and triazines. Moreover, the pigment illustrated later may be sufficient.

Anthraquinone and acridone may have a substituent such as 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 halogen such as chlorine. .
Triazine is an alkyl group such as methyl group or ethyl group, an amino group or dimethylamino group, an alkylamino group such as diethylamino group or dibutylamino group, a nitro group, a hydroxyl group, or an alkoxy group such as methoxy group, ethoxy group or butoxy group. And may have a substituent such as a halogen such as chlorine, a phenyl group, and 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.

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

General formula (3)

General formula (4)

General formula (5)

Each symbol in the general formulas (2) to (5) 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. Preferably it is 1-3.
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 typically has 2 to 36 carbon atoms. R ₁ and R ₂ are preferably each independently 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 groups represented by R ₃ typically have 1 to 36 carbon atoms. Also, the unsubstituted or substituted alkenyl group represented by R ₃ typically 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 preferably each independently 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 typically has 2 to 36 carbon atoms. R ₈ and R ₉ are 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.

P represents a substituent represented by the following general formula (6) or (7).
Q represents a hydroxyl group, an alkoxyl group, or a substituent represented by the following general formula (6) or (7). Q is preferably a substituent represented by the following general formula (6).

General formula (6)

一般式（６）および（７）において、Ｒ_１〜Ｒ_７、およびｎは、一般式（２）〜（４）に関して定義したとおりである。 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).

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. Unsubstituted or substituted alkyl groups represented by R ₁₀ , R ₁₁ , R ₁₂ , or R ₁₃ typically have 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.
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-Piperidin ethanol, 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.

Although the specific example of a pigment derivative is shown, it is not necessarily limited to these. These pigment derivatives can be used alone or in admixture of two or more.
Compound 1

Compound 2

Compound 3

  The blending amount of the pigment derivative in the pigment composition is preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the pigment. When the blending amount of the pigment derivative is less than 1 part by weight, the dispersion effect is insufficient, and when it is more than 20 parts by weight, the excess pigment derivative may affect the dispersion.

<Pigment>
As the pigment used in the present invention, organic or inorganic pigments may be used alone or in admixture of two or more.
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 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. 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.

<Pigment carrier>
The pigment carrier (A) used in 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 preferably has a transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. 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.

  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.

<Organic solvent>
In the pigment dispersion, the organic solvent used in the present invention sufficiently disperses the pigment in the pigment carrier, and in the colored composition, the dry film thickness is 0.2 to 5 μm on a transparent substrate such as a glass substrate. It is a component for making it easy to apply and form a 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.

<Pigment dispersion>
In the present invention, the pigment dispersion is obtained by mixing and dispersing at least a pigment, a pigment derivative, and a pigment carrier (A) composed of a transparent resin, a precursor thereof, or a mixture thereof. An Eiger mill etc. can be used for mixing and dispersion. The pigment dispersion may be filtered with a filter.

  In dispersing, an organic solvent can be used in order to sufficiently disperse the pigment in the pigment carrier (A). When the pigment is dispersed in the pigment carrier (A) and the organic solvent, a dispersion aid such as a resin-type pigment dispersant and 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.

  The resin-type 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 functions to adsorb to the pigment and stabilize the dispersion of the pigment on the pigment carrier. 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.

  These dispersing aids may be used alone or in combination of two or more. The dispersing aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment.

<Sonication>
The method for producing a colored composition of the present invention is characterized by ultrasonically treating a pigment dispersion. The pigment dispersion is well dispersed immediately after production, but if the storage state due to sale, storage, etc. is prolonged, agglomeration occurs and the dispersibility becomes poor. When a colored composition and a color filter are produced using such a pigment dispersion having poor dispersibility, the color filter is defective due to this.
Although the present invention can be applied to a pigment dispersion immediately after production, the quality of a coloring composition and a color filter using the same is significantly improved by subjecting the pigment dispersion that has been produced for a while to ultrasonic treatment. Has an effect.

The frequency in the ultrasonic treatment of the pigment dispersion is preferably 5 to 20 kHz.
In general, since an ultrasonic dispersion apparatus is small, it is difficult to uniformly disperse it when a large amount of processing is performed at once. Therefore, the ultrasonic treatment may be performed by reducing the processing amount at one time or by dividing it into several times.

  In general, heat generated from fine vibrations caused by ultrasonic waves may affect the pigment dispersion (pigment paste) itself or the state of a color resist completed by adding a coloring composition containing the pigment paste. is there.

In order to avoid this problem, as a further preferred embodiment of the present invention, a certain amount of the pigment dispersion has a configuration that passes through the ultrasonic wave generation portion at a constant speed.
In addition, if the dispersion effect of the pigment dispersion is small after passing through the ultrasonic wave generation portion only once, a plurality of ultrasonic devices may be prepared in the flow path, or the ultrasonic wave generation portion is repeatedly passed. May be.

In the case where the pigment dispersion is repeatedly passed through the ultrasonic wave generating portion, it is preferable to circulate through the channel where the pigment dispersion is closed by switching the channel and repeat the ultrasonic treatment as many times as necessary.
For example, a cup is placed under the ultrasonic generator so that a certain amount of pigment dispersion passes through the cup at a constant speed. When the pigment dispersion passes through the cup, ultrasonic waves are transmitted into the pigment dispersion, and this fine vibration destroys the pigment aggregation of the pigment dispersion to achieve redispersion.

  Further, a cooling device such as a water cooling tube can be attached to the ultrasonic processing part (for example, in the vicinity of the cup), and heat generation during the ultrasonic processing can be reduced.

  Furthermore, a pipe for flowing from the pigment dispersion tank to a raw material tank for other components used in the production of the colored composition is provided during the production of the colored composition, and an ultrasonic generator is provided in the middle of the inflow path. The pigment dispersion can be sonicated as it flows into the raw material tank. As described above, when the pigment dispersion is rapidly used in the production of a colored composition in a state where the pigment dispersion immediately after the ultrasonic treatment is good, a good colored composition can be obtained.

  Further, the discharge amount (flow rate) of the pigment dispersion at this time is preferably 30 kg / hr or less, although it depends on the viscosity of the pigment dispersion. By this ultrasonic treatment step, it is preferable that the viscosity of the pigment dispersion before the treatment is a state immediately after the production of the pigment dispersion or a value close to the state.

<Coloring composition>
The manufacturing method of the coloring composition of this invention is obtained by mixing a pigment dispersion and a pigment carrier (B). The pigment dispersion used at this time has been subjected to ultrasonic treatment before mixing with the pigment carrier (B). Since the pigment dispersion is preferably used in a state where the pigment particles are well dispersed, it is preferably used immediately after the ultrasonic treatment.

  The pigment carrier (B) is composed of a transparent resin and its precursor or a mixture thereof. Examples of the pigment carrier (B) include the same ones as described for the pigment carrier (A) used in the production of the pigment dispersion. It may be the same as that used in the pigment carrier (A) or may be different.

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 obtained by finely dispersing a pigment using various dispersing means in a pigment carrier and an organic solvent containing a thermoplastic resin, a thermosetting resin or a photosensitive resin and a monomer in the presence of a pigment derivative. It is.
The colored composition can also be produced by mixing several types of pigments separately dispersed in a pigment carrier and an organic solvent.

  The colored composition is mixed with the pigment carrier (B), and then classified by means such as filter filtration such as a sintered filter and a membrane filter, and centrifugal separation. Preferably, coarse particles of 5 μm or larger, more preferably coarse particles of 1 μm or larger, particularly preferably 0.5 μm or larger and mixed dust are removed. Filter filtration is preferably used.

When the colored composition obtained by the production method of the present invention is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the composition.
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.

  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.

<Color filter>
The color filter of the present invention is produced by forming filter segments of each color on a substrate by a photolithography method or a printing method using the colored composition (color filter coloring material) obtained by the production method of the present invention. be able to.
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 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 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. The printing is preferably a composition that does not dry or solidify the ink on the printing plate or on the blanket. Control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted with a dispersant or extender pigment.

  The formation of each color filter segment by the photolithography method 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 each Example and Comparative Example, the viscosity of the pigment dispersion and the filtration amount of the colored composition (colored resist material) were measured as follows.
Viscosity of pigment dispersion: BM type viscometer manufactured by RHEOMETRICS Colored resist material filtration amount: Amount of resist material that passed through 0.6 μm filter manufactured by Cuno Co., Ltd.In the examples and comparative examples, `` part '' is Means "parts by weight".
First, the acrylic resin solutions used in Examples and Comparative Examples will be described.

(Preparation of acrylic resin solution)
A reaction vessel was charged with 800 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
60.0 parts of styrene
Methacrylic acid 60.0 parts
Methyl methacrylate 65.0 parts
Butyl methacrylate 65.0 parts
Azobisisobutyronitrile 10.0 parts After the 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. The reaction was continued for 1 hour to obtain an acrylic resin solution having a weight average molecular weight of about 40,000.
After cooling to room temperature, about 2 g of the resin solution was sampled, 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 parts. An acrylic resin solution was prepared.

[Example 1]
(Red resist material)
After uniformly stirring and mixing a mixture having the following composition as a pigment dispersion, the mixture was dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, then filtered through a 1.0 μm filter, and a diketo for red resist material. A pyrrolopyrrole dispersion (pigment dispersion) was prepared.
Diketopyrrolopyrrole red pigment CI Pigment Red 254 10.0 parts ("Irga Four Red B-CF" manufactured by Ciba Geigy)
Anthraquinone pigment derivative 1.0 part Dispersing aid ("Solspers 20000" manufactured by Zeneca) 1.0 part Acrylic resin solution 40.0 parts Cyclohexanone 48.0 parts Sonication was performed with a disperser (processing conditions: frequency 15 kHz, discharge rate about 8 kg / hr, total amount passed 4 times). Subsequently, a mixture having the following composition was stirred and mixed so that a red resist material (colored composition before filtration) was obtained.
Diketopyrrolopyrrole-based dispersion for red resist (ultrasonic treatment) 45.0 parts Acrylic resin solution 15.0 parts Trimethylolpropane triacrylate ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) 5.6 parts Photopolymerization Initiator 2.0 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part Cyclohexanone 32.2 parts

[Comparative Example 1]
A red resist material was obtained in the same manner as in Example 1 except that the pigment dispersion which was allowed to stand for 3 months after production was not dispersed with ultrasonic waves.

  The viscosity of the pigment dispersion of Example 1 was 10.0 cP, and the viscosity of the pigment dispersion of Comparative Example 1 was 14.4 cP. Moreover, the filtration amount of the red resist material of Example 1 was 240 g, and the filtration amount of the red resist material of Comparative Example 1 was 175 g.

[Example 2]
(Green resist material)
A diketopyrrolopyrrole red pigment and an anthraquinone pigment derivative are combined with a phthalocyanine green pigment (CI pigment green 36) ("Lionol Green 6Y-501" 10.0 parts, manufactured by Toyo Ink Co., Ltd.), phthalocyanine A green resist material (before filtration) was prepared in the same manner as the red resist material except that the pigment derivative was changed to 1.0 part.

[Comparative Example 2]
A green resist material was obtained in the same manner as in Example 2 except that the pigment dispersion which was allowed to stand for 3 months after production was not dispersed with ultrasonic waves.
The viscosity of the pigment dispersion of Example 2 was 8.4 cP, and the viscosity of the pigment dispersion of Comparative Example 2 was 15.3 cP. Moreover, the filtration amount of the green resist material of Example 2 was 325 g, and the filtration amount of the green resist material of Comparative Example 2 was 200 g.

[Comparative Example 3]
(Blue resist material)
Diketopyrrolopyrrole red pigment and anthraquinone pigment derivative are combined with 10.0 parts of ε-type copper phthalocyanine pigment (CI pigment blue 15: 6) (“Heliogen Blue L-6700F” manufactured by BASF), phthalocyanine series A green resist material was prepared in the same manner as the red resist material except that the pigment derivative was changed to 1.0 part.

[Comparative Example 3]
A blue resist material was obtained in the same manner as in Example 3 except that the pigment dispersion which was allowed to stand for 3 months after the production was not dispersed with ultrasonic waves.

  The viscosity of the pigment dispersion of Example 3 was 8.5 cP, and the viscosity of the pigment dispersion of Comparative Example 3 was 9.7 cP. Moreover, the filtration amount of the blue resist material of Example 3 was 206.6 g, and the filtration amount of the blue resist material of Comparative Example 3 was 134.4 g.

  When producing a colored composition by dispersing pigment particles, there is a certain restriction on the particle size of the pigment and the type of the dispersant because it must be finally filtered with a filter having a small pore size. Even if it is necessary to use a pigment paste that has been finely divided to produce a color resist with specific characteristics or a pigment paste that has agglomerated because the amount of the dispersant is not appropriate, the method of the present invention provides sufficient color. As a resist, stability is obtained.

Claims (5)

After ultrasonically treating a pigment dispersion obtained by mixing and dispersing a pigment, a pigment derivative, and a pigment carrier (A) composed of a transparent resin, a precursor thereof or a mixture thereof,
A method for producing a coloring composition, which is mixed with a pigment carrier (B) and filtered.   The method for producing a coloring composition according to claim 1, wherein the ultrasonic dispersion is repeatedly performed by circulating the closed channel through which the pigment dispersion is closed. Piping is introduced from the pigment dispersion tank to the raw material tank for other components used in the production of the coloring composition,
An ultrasonic generator is installed in the middle of the inflow path,
The method for producing a colored composition according to claim 1, wherein the pigment dispersion is subjected to ultrasonic treatment when flowing into the raw material tank.   A colored composition obtained by the production method according to claim 1.   A color filter comprising a filter segment formed using the colored composition according to claim 4.