JP6561500B2 - Method for producing coloring composition for color filter, coloring composition for color filter, and color filter - Google Patents

Description

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

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display by using a twisted nematic (TN) type liquid crystal. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

  A quality item required for the color filter is a contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

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

In general, it is difficult to obtain a stable coloring composition by dispersing fine pigment particles in a colorant carrier such as varnish in the pigment dispersion method, and the pigment particles therein often aggregate over time. A color filter formed using a coloring composition in which pigment particles are aggregated significantly reduces the contrast ratio. Therefore, the pigment may be stable fine particles without agglomeration in the pigment, and may be easily handled. It is desired.
Furthermore, in recent years, required properties such as contrast ratio and flow stability required for a color filter coloring composition have become very high performance, and a technique for finely dispersing pigments is important.

In the fine dispersion of pigment, generally, in a disperser called a sand mill, a sand grinder, a dyno mill, a pearl mill, etc., the pigment composition is processed by impact force, shear force, friction force obtained by vigorously stirring the media with a stirring mechanism. Is done by.
Further, as a method of finely dispersing the pigment, using a media stirring type disperser, without using a pigment derivative, only the pigment is dispersed in multiple stages, and the diameter of the media in each stage is sequentially reduced, and A method of performing dispersion in a circulation has been proposed (see, for example, Patent Document 1).
Further, it has been proposed that a pigment dispersion having a very high contrast and good fluidity can be obtained by using a fine media having a media diameter of 0.3 mmφ or less for a media stirring type disperser (for example, Patent Document 2). reference).

Micro media is attracting attention as an effect of solving the aggregation of particles because the kinetic energy of each medium is very small. However, if the mill base is not uniform, the effect is lost in the mixing and the original fine dispersion effect is not utilized. In addition, the effect is not utilized in the same way unless the particles are dispersed so as to make the particles finer to some extent.
On the other hand, in multi-stage dispersion using media, before the recent finer pigments are finely dispersed to the submicron range, the media is pulverized faster than the adsorption rate of resin-type dispersants, etc. Damages the pigment surface to form strong aggregates, which causes a significant destabilization of the viscosity.
Then, although the manufacturing method which suppressed the aggregate by the multistage dispersion process using the high-speed shearing disperser which does not have a media is proposed, it is not examined by the combination with the dispersion | distribution using a micro media (for example, patent document 3). reference). If the dispersion using fine media as described above is not performed, a remarkable fine dispersion effect cannot be obtained, and this manufacturing method does not satisfy the target quality.

JP 11-352319 A JP 2005-221804 A JP 2009-86061 A

  The present invention eliminates coarse particles that adversely affect quality by classification processing in order to make use of fine media dispersion, and also produces a mill base that is good at fine media, and performs fine media dispersion with low media specific gravity in the next process. The purpose is to achieve both high contrast and viscosity stability by dispersing to a submicron region of 1 μm or less without generating a particle interface.

  In the conventional first dispersion step by media dispersion performed stepwise, the kinetic energy of the media is large, and fine particles are generated before the particle size becomes sharp, so that the viscosity stability deteriorates. In the second dispersion step, the kinetic energy of the media is small, and the particle interface is not damaged, but the strong aggregate in which coarse particles and fine particles are aggregated cannot be dispersed. The inventors of the present invention assume that coarse particles are present in the mill base only in the first dispersion step by classification treatment, and the classified fine particles are used as a mill base dispersion in the second dispersion step, so that a loss-free dispersion step can be performed. Focusing on the fact that it can be built, it has been found that a colored composition having a high contrast and a stable viscosity can be obtained, and the present invention has been completed.

That is, the present invention is a method for producing a colored composition comprising at least a colorant, a resin, and a solvent,
In a media type disperser having a media in the range of 0.2 to 2.0 mmφ, a mill base containing a colorant, a resin, and a solvent is subjected to a dispersion treatment so that the average particle diameter of the colorant is 1 μm or less. The dispersion liquid dispersed in the dispersion process
Classification by a high-speed centrifugal force into a dispersion having particles having an average particle size of more than 1 μm and a dispersion having particles of 1 μm or less;
The dispersion having particles larger than 1 μm is returned to the first dispersion step;
The dispersion having particles of 1 μm or less is a media-type disperser having media in the range of 0.005 to 0.1 mmφ, and is continuously dispersed in a second dispersion step of dispersion treatment. The present invention relates to a method for producing a colored composition for a filter.

  The present invention also relates to the method for producing a colored composition for a color filter, wherein the disperser used in the second dispersion step includes a media separation mechanism by centrifugation.

  Moreover, this invention relates to the manufacturing method of the said coloring composition for color filters whose classifier is classified by high speed centrifugation.

  Moreover, this invention relates to the manufacturing method of the said coloring composition for color filters characterized by the centrifugal force of a classifier being 4000-7000 (xg).

  Moreover, this invention relates to the manufacturing method of the said coloring composition for color filters characterized by the discharge amount of a classifier being 20-40 kg / h.

  Moreover, this invention relates to the coloring composition for color filters manufactured by the said method.

  The present invention further relates to the coloring composition for a color filter, further comprising a photopolymerization initiator.

  Moreover, this invention relates to the color filter characterized by including the filter segment formed using the said coloring composition for color filters.

  According to the production method of the present invention, it is possible to stably finely disperse a pigment dispersion that has been easily re-aggregated so far, and to obtain a colored composition for a color filter having a low viscosity and a stable viscosity over time. Moreover, a color filter with a high contrast ratio can be obtained by using the coloring composition for a color filter.

Hereinafter, the present invention will be described in detail.
A method for producing a colored composition containing at least a colorant, a resin, and a solvent, wherein the average particle size of the pigment is 1 μm or less in a media-type disperser having media in the range of 0.2 to 2.0 mmφ. The dispersion dispersed in the first dispersion step is subjected to high-speed centrifugal force to classify the dispersion into a dispersion having particles having an average particle diameter of more than 1 μm and a dispersion having particles of 1 μm or less, and the above-mentioned 1 μm. The dispersion liquid having larger particles is returned to the first dispersion step, and the dispersion liquid having particles of 1 μm or less is subjected to dispersion treatment with a media type disperser having media in the range of 0.005 to 0.1 mmφ. It is characterized in that it is continuously dispersed in two dispersion steps.

  As a classifier in the present invention, it is only necessary to classify particles in a state containing a solvent, and KRETTEK micro cut, Okawara Seiko cyclone, etc. characterized by classification by a centrifugal separation mechanism can be used. In addition, a sieving type classifier has been developed as a classifier, but classification in a very fine region such as 1 μm requires a classifier using a centrifugal mechanism with increased centrifugal force at high speed.

  In the present invention, the dispersion having particles larger than 1 μm is returned to the first dispersion step. In addition to obtaining the effect of performing the second dispersion step with only particles of 1 μm or less, this is a stable composition that can be applied to both continuous and batch processes and is stable in process control. Can be given.

  Media-type dispersers include cylindrical dispersers of horizontal, vertical, and annular (annular) types. For example, various dispersers that use media such as ball mills, sand mills, attritors, and vibration mills are used. it can.

The rotating shaft of this media type disperser is provided with stirring blades having various shapes, and disk type, pin type, etc. are known. Among them, those equipped with rotor pins are effective for the present invention. Preferred to make it even more pronounced.
In addition, as a media separation mechanism of this media type dispersing machine, there are a centrifugal separation method, a slit method (gap separator method), a screen method, and the like, but a centrifugal separation method is preferable. The production of slits or screens that can separate minute media with a particle size of 0.1 mmφ or less is very difficult due to machining accuracy, and may cause clogging when supplying a mill base pigment dispersion. is there.

Examples of wet dispersers equipped with a rotor pin and a media separation mechanism by centrifugation include, for example, a super apex mill (manufactured by Kotobuki Industries), an ultra apex mill (manufactured by Kotobuki Industries), a dual apex mill (manufactured by Kotobuki Industries), and a DCP type. There are a pearl mill (manufactured by Eirich), a picogren mill (manufactured by Asada Iron Works), and an eco mill (manufactured by Asada Iron Works).
Moreover, the media filling rate in the disperser with good dispersion efficiency is preferably 50 to 100% by volume, more preferably 60 to 80% by volume.
The material of the media is not particularly limited, and commonly used glass, steel, stainless steel, ceramics, zircon, zirconia and the like can be mentioned. The media particle size must be 0.1 mmφ or less in order to achieve fine dispersion, a sizing effect, and a high contrast ratio. In particular, when using a micro media of 0.05 mmφ to 0.005 mmφ, the effect is It is preferable because it becomes very large.

Next, raw materials that are supplied to the disperser and constitute the color filter coloring composition will be described.
(Coloring agent)
As the colorant contained in the coloring composition of the present invention, organic or inorganic pigments can 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 for color filters of this invention is shown with a color index number.

When forming a red filter segment using the coloring composition of the present invention, for example, C.I. I. 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, 166, 168, 176, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 240, Red pigments such as 242, 246, 254, 255, 264, 269, and 272 can be used.
The red coloring composition includes C.I. I. Pigment Orange 36, 38, 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like.

When forming a green filter segment using the coloring composition of the present invention, for example, C.I. I. Examples thereof include, but are not limited to, aluminum phthalocyanine pigments described in CI Pigment Green 7, 10, 36, 37, 58, 59, JP-A No. 2004-333817, and Japanese Patent No. 4893859.
The green coloring composition includes C.I. I. 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, 167, 168, 169, 170, 171, 172, 173, 174, 175, 1 It can be used in combination with the yellow pigments such as 6,177,179,180,181,182,185,187,188,193,194,199,213,214.

When forming a blue filter segment using the coloring composition of the present invention, for example, C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used.
The blue coloring composition includes C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

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 And synthetic iron black. 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.
The colorant used in the present invention contains the pigment, but in addition, for color matching, a dye may be contained within a range in which the heat resistance is not lowered.

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

  In order to disperse or dissolve the colorant preferably, the weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the resin is used for a color filter coloring composition, from the viewpoint of dispersibility, stability, developability, and heat resistance of the photosensitive coloring composition, as a colorant adsorbing group and an alkali-soluble group during development. The balance of working carboxyl groups, aliphatic groups and aromatic groups acting as affinity groups for the colorant carrier and solvent is important for the dispersibility, penetrability, developability and even durability of the pigments and salt-forming compounds, It is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, no fine pattern remains.

Since the resin has good film formability and various resistances, the resin is preferably used in an amount of 30% by weight or more based on the total weight of the colorant (100% by weight), and has a high colorant concentration and good color. Since the characteristics can be expressed, it is preferably used in an amount of 500% by weight or less.
(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter with high contrast can be obtained.

(Pigment derivative)
The pigment derivatives are compounds 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 pigment residue B: Basic substituent or acidic substituent

  In the general formula (1), the organic pigment constituting the organic pigment residue of A includes diketopyrrolopyrrole pigments, azo pigments such as azo, disazo and polyazo, copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine. Phthalocyanine pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indantron, pyranthrone, violanthrone, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, Examples thereof include thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

式（３）

式（４）

式（５）

式（６）

式（７）

In the general formula (1), examples of the basic substituent of B include substituents represented by the following formula (2), formula (3), formula (4), and formula (5). Includes substituents represented by formula (6) and formula (7).
Formula (2)

Formula (3)

Formula (4)

Formula (5)

Formula (6)

Formula (7)

X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ : each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, or R ₁ and R ₂ together represent an optionally substituted heterocycle containing an additional nitrogen, oxygen or sulfur atom.
R ₃ represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R ₄ , R ₅ , R ₆ , R ₇ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or a substituent Represents an optionally substituted phenyl group.
Y: represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Represents.
Z: represents an optionally substituted alkylene group having 1 to 36 carbon atoms, an optionally substituted alkenylene group having 2 to 36 carbon atoms, or an optionally substituted phenylene group.

式（９）

R: The substituent shown by Formula (8) or the substituent shown by Formula (9) is represented.
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the formula (8) or a substituent represented by the formula (9).
Formula (8)

Formula (9)

M: represents a hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom or aluminum atom.
i: represents the valence of M.
R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, substitution Represents an optionally substituted phenyl group or polyoxyalkylene group.

  Examples of the amine component used for forming the substituent represented by the formulas (2) to (5), the formula (8), and the formula (9) include dimethylamine, diethylamine, N, N-ethylisopropyl, and the like. Amine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine N, N-methyloctadecylamine, didecylami Diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N , N-dimethylaminoamylamine, 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 −Me Rulaurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3 -Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinemethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetinate, Ethyl isonicopetic acid, 2-Piperidinethanol, Pyrrolidine 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4- Examples include pipecoline, N-aminopropylmorpholine, 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 (7) may be any of primary, secondary, tertiary and quaternary amines. For example, primary amines have side chains. Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, Examples include amines such as eocosylamine, or unsaturated amines corresponding to the number of carbon atoms.

Secondary, tertiary and quaternary amines include dioleylamine, distearylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmonomethylamine, trioctylamine, dimethyldidodecylammonium 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, trimethyl octadecyl ammonium chloride, dimethyl dodecyl tetradecyl ammonium chloride , Dimethyl hexadecyl octadec Ammonium chloride, and the like.
Further, when any of R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in the formula (7) represents a polyoxyalkylene group, examples thereof include a polyoxyethylene group and a polyoxypropylene group.

ＣｕＰｃは、銅フタロシアニン残基を表す。


化合物２

化合物３

Specific examples of pigment derivatives are shown below with compound numbers.
Compound 1

CuPc represents a copper phthalocyanine residue.


Compound 2

Compound 3

化合物５

化合物６

Compound 4

Compound 5

Compound 6

化合物８

化合物９

Compound 7

Compound 8

Compound 9

  The blending amount of the pigment derivative in the coloring 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.

(Resin type dispersant)
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 phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) 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.
Specifically, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174 manufactured by Big Chemie Japan Co., Ltd. , 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S , 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc., SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, manufactured by Lubrizol Japan 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., manufactured by Ciba Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330 , 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101 120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; poly Oxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbita Nonionic surfactants such as monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine, alkylimidazolines, etc. These amphoteric surfactants can be used, and these can be used alone or in admixture of two or more.

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

(Other additive components)
Further, the color filter coloring composition can contain a storage stabilizer in order to stabilize the viscosity with time. Examples of storage stabilizers 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. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the colorant in the coloring composition (100% by weight).
(Removal of coarse particles and dust)
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that the coloring composition for color filters substantially does not contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

(solvent)
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. A solvent can be included to facilitate formation.
Examples of the solvent include benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3 -Butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m -Dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-alkyl Silene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene Glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol mono Hexyl ether, ethylene glycol monomethyl ether , Ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone , Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipro Lenglycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether , Propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, vinegar Isobutyl, propyl acetate, dibasic esters, butyl lactate and the like.

  Among them, since the dispersibility of the colorant of the present invention is good, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, benzyl alcohol, etc. It is preferable to use ketones such as aromatic alcohols and cyclohexanone. Moreover, a solvent can be used individually by 1 type or in mixture of 2 or more types.

Next, the raw material which comprises the photosensitive coloring composition for color filters is demonstrated.
(Thermoplastic resin)
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

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

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

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

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

Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

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

  As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

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

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

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

(Thermosetting resin)
Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
The colored composition of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

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

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

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

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or ben Benzoin compounds such as rudimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphene) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and other oxime ester compounds; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.

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

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

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

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

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” means “parts by weight”.
Prior to the examples, a method for measuring the contrast ratio of the colored composition-coated substrate will be described.
The coloring composition-coated substrate is sandwiched between two polarizing plates, and light is irradiated from one polarizing plate side using a backlight unit for liquid crystal display. The light emitted from the backlight unit passes through the first polarizing plate and is polarized, and then passes through the resist material-coated substrate and reaches the second polarizing plate. If the polarization planes of the first polarizing plate and the second polarizing plate are parallel, the light passes through the second polarizing plate, but if the polarization plane is perpendicular, the light passes through the second polarizing plate. Are blocked by the polarizing plate. However, when the light polarized by the first polarizing plate passes through the resist material coated substrate, scattering by pigment particles or the like causes a deviation in a part of the polarization plane. When the amount of light transmitted through the second polarizing plate is reduced and the deflecting plate is perpendicular, a part of the light is transmitted through the second polarizing plate. This transmitted light is measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plate is parallel and the luminance when the polarizing plate is orthogonal is defined as the contrast ratio.
Contrast ratio = (Luminance when parallel) / (Luminance when direct)

Accordingly, when scattering occurs due to the pigment in the colored composition coating film, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered.
The luminance meter was a color luminance meter BM-5A manufactured by Topcon Corporation, and the polarizing plate was a polarizing film LLC2-92-18 manufactured by Sanritsu. In the measurement, in order to block unnecessary light, measurement was performed by applying a black mask having a 1 cm square hole in the measurement portion.

"Average particle size"
The dispersion dispersed in the first dispersion step was measured by an in-line particle size distribution analyzer Insitec made by Malvern Co., Ltd. to obtain an average particle size.
"Initial viscosity"
The viscosity at 25 ° C. of each colored composition of Examples 1 to 31 and Comparative Examples 1 to 4 was measured using an E-type viscometer (TVE-20L type manufactured by TOKI SANGYO) at a rotation speed of 20 rpm.
"Viscosity stability"
Furthermore, the viscosity (hereinafter referred to as time-dependent viscosity) accelerated at 40 ° C. for 1 week was measured in the same manner, and the difference was measured to determine the viscosity stability (time-dependent viscosity−initial viscosity).

The adjustment of the acrylic resin solution used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
(Preparation of acrylic resin solution)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Addition to prepare an acrylic resin solution.
Here, the polymerization average molecular weight (Mw) of the acrylic resin was measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. The weight average molecular weight (Mw) in terms of polystyrene.

The classification after the first dispersion step was performed using the following classifiers 1-4.
Classifier 1. Centrifugal classifier Microcut classifier manufactured by KRETTEK Centrifugal classifier Cyclone classifier manufactured by Okawara Seisakusho 3. Centrifugal classifier Super cron classifier manufactured by Murata Kogyo Co., Ltd. AS200 manufactured by Lecce

(Preparation of colored composition)
Example 1
When the following mixture was dispersed for 3 hours with a super apex mill manufactured by Kotobuki Industries Co., Ltd. using zirconia beads having a diameter of 0.5 mm (first dispersion step), the average particle size was 1 μm or less, and therefore, listed in Table 1 Classification was started using the classifier and classification conditions. After the first dispersion step, the dispersion classified as coarse particles having a particle size of more than 1 μm is returned to the first dispersion step, subjected to additional dispersion for 1 hr and classified again under the same conditions, and classified as coarse particles. Since the dispersion thus obtained was 1.0% by weight or less of the returned mill base, it was set as the end point of the first dispersion step. Dispersed particles classified as fine particles having a size of 1 μm or less in the first dispersion step were dispersed for 1 hr in an ultra apex mill manufactured by Kotobuki Industries Co., Ltd. using zirconia beads having a diameter of 0.03 mm (second dispersion) Step), 20.5 parts of propylene glycol monomethyl ether acetate (PGMAC) was added and diluted, and then filtered through a 1.0 μm filter to obtain a red colored composition (RP-1).
Red pigment (CI Pigment Red 254): 20.0 parts acrylic resin solution: 36.0 parts propylene glycol monomethyl ether acetate (PGMAC): 19.5 parts resin type dispersant “EFKA4300” manufactured by Ciba Japan Co., Ltd .: 4.0 parts
(Examples 2-7, Examples 13-16)
Except having changed the classification conditions as described in Table 1, red colored compositions (RP-2 to RP-7, RP-10 to RP-13) were obtained in the same manner as in Example 1, respectively.
(Examples 8 to 9)
Red colored compositions (RP-8 to RP-9) were obtained in the same manner as in Example 1 except that the media diameter of the zirconia beads in the second dispersion step was changed as described in Table 1.
(Example 10)
When the following mixture was dispersed for 2 hr in a super apex mill manufactured by Kotobuki Industries Co., Ltd. using zirconia beads having a diameter of 0.5 mm (first dispersion step), the average particle size was 1 μm or less, and therefore listed in Table 1. Classification was started using the classifier and classification conditions. After the first dispersion step, the dispersion classified as coarse particles having a particle size larger than 1 μm is returned to the first dispersion step, and after additional dispersion is performed for 0.5 hr, classification is performed again under the same conditions. The dispersion thus classified was 1.0% by weight or less of the returned mill base, so that the end point of the first dispersion step was set as the end point. In the first dispersion step, the dispersion classified as fine particles having a size of 1 μm or less is dispersed into a dispersion obtained by performing dispersion for 2 hours with an ultra apex mill manufactured by Kotobuki Industries Co., Ltd. using zirconia beads having a diameter of 0.03 mm (second dispersion). Step), 20.5 parts of propylene glycol monomethyl ether acetate (PGMAC) was added and diluted, and then filtered through a 1.0 μm filter to obtain a green colored composition (GP-1).
Green pigment (CI Pigment Green 58): 20.0 parts acrylic resin solution: 38.0 parts propylene glycol monomethyl ether acetate (PGMAC): 18.0 parts resin type dispersant ("BYK-111" manufactured by BYK Chemie) ): 3.5 parts (Example 11)
When the following mixture was dispersed for 1 hr in a super apex mill manufactured by Kotobuki Industries Co., Ltd. using zirconia beads having a diameter of 0.5 mm (first dispersion step), the average particle size was 1 μm or less, and therefore listed in Table 1. Classification was started using the classifier and classification conditions. After the first dispersion step, the dispersion classified as coarse particles having a particle size larger than 1 μm is returned to the first dispersion step, and after additional dispersion is performed for 0.5 hr, classification is performed again under the same conditions. The dispersion thus classified was 1.0% by weight or less of the returned mill base, so that the end point of the first dispersion step was set as the end point. Dispersed particles classified as fine particles having a size of 1 μm or less in the first dispersion step were dispersed for 1 hr in an ultra apex mill manufactured by Kotobuki Industries Co., Ltd. using zirconia beads having a diameter of 0.03 mm (second dispersion) Step), 20 parts of propylene glycol monomethyl ether acetate (PGMAC) was added and diluted, and then filtered through a 1.0 μm filter to obtain a blue colored composition (BP-1).
Blue pigment (C.I. Pigment Blue 15: 6): 18.0 parts acrylic resin solution: 42.3 parts cyclohexanone: 16.1 parts resin-type dispersant ("BYK-111" manufactured by BYK Chemie): 3.6 (Example 12)
When the following mixture was dispersed for 1.5 hr in a super apex mill manufactured by Kotobuki Industries Co., Ltd. using zirconia beads having a diameter of 0.5 mm (first dispersion step), the average particle size became 1 μm or less. Classification was started with the classifier and classification conditions described in 1. After the first dispersion step, the dispersion classified as coarse particles having a particle size larger than 1 μm is returned to the first dispersion step, and after additional dispersion is performed for 0.5 hr, classification is performed again under the same conditions. The dispersion thus classified was 1.0% by weight or less of the returned mill base, so that the end point of the first dispersion step was set as the end point. Dispersed particles classified as fine particles having a size of 1 μm or less in the first dispersion step were dispersed for 1 hr in an ultra apex mill manufactured by Kotobuki Industries Co., Ltd. using zirconia beads having a diameter of 0.03 mm (second dispersion) Step), 21.7 parts of propylene glycol monomethyl ether acetate (PGMAC) was added and diluted, and then filtered through a 1.0 μm filter to obtain a yellow colored composition (YP-1).
Yellow pigment (CI Pigment Yellow 150): 20.0 parts acrylic resin solution: 38.5 parts propylene glycol monomethyl ether acetate (PGMAC): 15.6 parts resin-type dispersant ("BYK-111" manufactured by BYK Chemie) : 4.2 parts
(Comparative Example 1)
A red colored composition RP-14 was obtained in the same manner as in Example 1 except that the classification conditions were changed to the conditions shown in Table 1.
(Comparative Example 2)
A red colored composition RP-15 was obtained in the same manner as in Example 1 except that the second dispersion step was changed to the conditions described in Table 1.

(Preparation of photosensitive coloring composition)
(Examples 17 to 25, Examples 28 to 31)
The red photosensitive coloring compositions (RR-1 to RR-) were mixed in proportions shown in Table 3 and corresponding to the red coloring compositions (RP-1 to RP-9, RP-10 to RP-13). 9, RR-10 to 13).
(Example 26)
The green photosensitive coloring composition (GR-1) was obtained by mixing at the ratio shown in Table 3.
(Example 27)
A blue photosensitive coloring composition (BR-1) was obtained by mixing at the ratio shown in Table 3.
(Comparative Examples 3-4)
The red photosensitive coloring compositions (RR-14 to RR-15) were respectively obtained corresponding to the red photosensitive coloring compositions (RP-14 to RP-15) by mixing at the ratios shown in Table 3.

(Production of color filter)
(Example 32)
A black matrix is patterned on a glass substrate, and the red photosensitive coloring composition RR-1 is applied to the substrate with a spin coater in a C light source (hereinafter also used for green and blue) x = 0.640, y = 0 The film was applied to a film thickness of about 330 to form a colored film. The film was irradiated with ultraviolet rays of 300 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the green photosensitive coloring composition GR-1 is formed to a thickness such that x = 0.300 and y = 0.600, and the blue photosensitive coloring composition BR-1 is used. 150 and y = 0.06 were respectively applied to form a green filter segment and a blue filter segment to obtain a color filter.

[Evaluation of Examples 1 and 6 to 7, Comparative Example 1 and Examples 17, 22 to 23, and Comparative Example 3]
As shown in Table 2, in the method for producing a red colored composition, the classifier had good contrast ratio and viscosity stability in the order of Example 1 = Example 6 = Example 7> Comparative Example 1. The target classified particle size is very fine as 1 μm. In the classifier of the sieving type, the classification efficiency is lowered, and coarse particles cannot be classified, and the target quality cannot be obtained. Moreover, as shown in Table 4, the photosensitive coloring composition using them also had a high contrast ratio and good viscosity stability (RR-1, RR-6 to RR-7).

[Evaluation of Examples 4-5, 15-16 and Examples 20-21, 30-31]
As shown in Table 2, in the method for producing a red colored composition, the centrifugal force of classification was good in contrast ratio and viscosity stability in the order of Example 4 = Example 5> Example 16> Example 15. When the centrifugal force exceeds 7000 (× g), fine particles of 1 μm or less have been classified together with coarse particles. Further, when the coarse particles were less than 4000 (× g), the centrifugal effect was small and the effect of classifying the coarse particles was small, so that the ability of fine bead dispersion in the second dispersion step could not be sufficiently drawn out. Moreover, as shown in Table 4, the photosensitive coloring compositions using them also had a high contrast ratio and good viscosity stability (RR-4 to RR-5, RR-12 to RR-13).

[Evaluation of Examples 2-3, Examples 13-14, Examples 18-19, and Examples 28-29]
As shown in Table 2, the flow rate of classification in the method for producing a red colored composition was good in contrast ratio and viscosity stability in the order of Example 2 = Example 3> Example 13> Example 14. When the flow rate is lower than 20 kg / h, the discharge from the classifier becomes a pulsating flow, and the classification performance at the target particle diameter is low. On the contrary, when the flow rate is higher than 40 kg / h, coarse particles are classified. Both of them were discharged from the machine, and neither of them was able to bring out the ability of fine bead dispersion in the second dispersion step. Moreover, as shown in Table 4, the photosensitive coloring composition using them also had a high contrast ratio and good viscosity stability (RR-2 to RR-3, RR-10 to RR-11).

[Evaluation of Examples 8 to 9, Comparative Example 2 and Examples 24 to 25, and Comparative Example 4]
As shown in Table 2, in the method for producing a red coloring composition, the dispersion bead diameter in the second dispersion step was good in contrast ratio and viscosity stability in the order of Example 8 = Example 9> Comparative Example 2. Since coarse particles are removed after classification, if the dispersion is performed with beads having a diameter of 0.05 mmφ or less, a very excellent product quality with no particle interface can be obtained. Moreover, as shown in Table 4, the photosensitive coloring compositions using them also had a high contrast ratio and good viscosity stability (RR-8 to RR-9).

[Evaluation of Examples 10-12 and 26-27]
As shown in Table 2, when the disperser 1 is used in the method for producing the green coloring composition, the blue coloring composition, and the yellow coloring composition, both the contrast ratio and the viscosity stability are achieved in the same manner as the red coloring composition. Quality was obtained (GP-1, BP-1, YP-1). The photosensitive coloring composition using them also had a high contrast ratio and good viscosity stability (GR-1, BR-1).

Claims (6)

A method for producing a colored composition comprising at least a colorant, a resin, and a solvent,
In a media-type disperser having a media in the range of 0.2 to 2.0 mmφ, the dispersion dispersed in the first dispersion step in which the average particle size of the colorant is dispersed to be 1 μm or less,
Classification by a high-speed centrifugal force into a dispersion having particles having an average particle size of more than 1 μm and a dispersion having particles of 1 μm or less;
The dispersion having particles larger than 1 μm is returned to the first dispersion step;
The dispersion having particles of 1 μm or less is a media-type disperser having media in the range of 0.005 to 0.1 mmφ, and is continuously dispersed in a second dispersion step of dispersion treatment. The manufacturing method of the coloring composition for filters. The method for producing a colored composition for a color filter according to claim 1, wherein the disperser used in the second dispersion step includes a media separation mechanism by centrifugation. The centrifugal force of a classifier is 4000-7000 (xg), The manufacturing method of the coloring composition for color filters of Claim 1 or 2 characterized by the above-mentioned. The discharge rate of a classifier is 20-40 kg / h, The manufacturing method of the coloring composition for color filters in any one of Claims 1-3 characterized by the above-mentioned. Furthermore, a photoinitiator is contained, The manufacturing method of the coloring composition for color filters of Claims 1-4 characterized by the above-mentioned. A method for producing a color filter, comprising a filter segment formed by using the color filter coloring composition produced by the production method according to claim 5.