JP2018172542A - Colorant dispersant, colorant, coloring resin composition, color filter, and display device - Google Patents

Abstract

Disclosed is a colorant dispersion that is excellent in heat resistance and capable of forming a colored layer having a high brightness and a reduced thickness.
A coloring material, a dispersant, and a solvent are contained, and the coloring material contains a salt forming coloring material of a yellow dye. In the salt forming coloring material of the yellow dye, the yellow dye is cationic. In some cases, the colorant dispersion is such that when the counter ion is a heteropolyacid anion and the yellow dye is anionic, the counter ion is a cation derived from a polymetal salt.
[Selection figure] None

Description

  The present invention relates to a color material dispersion, a color material, a colored resin composition, a color filter, and a display device.

The color filter is usually a pattern in which pixels of three colors of red, blue and green are formed on a transparent substrate. In order to improve color reproducibility, display products using a color filter in which pixels of four colors obtained by adding yellow to the three colors are formed in a pattern have been put on the market in recent years. Moreover, in a red pixel and a green pixel, in order to obtain desired chromaticity, a yellow color material may be mixed.
Under such circumstances, there is an increasing demand for higher brightness and higher contrast of color filters, and improved color reproducibility. In particular, there is a demand for higher brightness of colored pixels containing yellow color materials. Yes.

  As a method for forming a pixel in a color filter, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like are known. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.

In a color filter having pixels formed by using a pigment dispersion method, miniaturization of pigments is being studied in order to achieve high brightness and high contrast. By making the pigment finer, it is considered that the scattering of light transmitted through the color filter by the pigment particles is reduced, and high brightness and high contrast are achieved. However, the refined pigment particles have a problem of being easily aggregated.
In addition, yellow pigments on the market that have relatively high luminance have a problem in that it is difficult to reduce the thickness of the colored layer because the coloring power is low and a large amount of pigment must be contained in the colored layer. It was.

  Therefore, from the viewpoint of further increasing the brightness of the color filter, a color resin composition for a color filter using a dye having a high transmittance is generally studied. However, since dyes have poor heat resistance and light resistance compared to pigments, the chromaticity is likely to change during high-temperature heating and light irradiation in the color filter manufacturing process, and the brightness of the colored layer is likely to decrease. was there. In addition, the colored resin composition using the dye has a problem that foreign matters are likely to be deposited on the surface of the cured coating film in the drying step, and has many problems when used as a color filter.

  Patent Document 1 discloses that a colored composition containing a yellow colorant is excellent in resistance to color characteristics, heat resistance, and the like, has no foreign matter generation on the coating film, and is stable in the side chain. It has been proposed to use a salt-forming compound that can be obtained by a reaction between a group-containing resin and a quinophthalone-based acidic compound.

JP 2014-21139 A

  However, the colorant described in Patent Document 1 has insufficient heat resistance, discoloration after post-baking when forming a colored layer, and the problem of decreased brightness and insufficient stability, There is a problem that foreign matter is generated when a coating film is produced. Furthermore, since the coloring agent described in Patent Document 1 has low coloring power and needs to contain a large amount of coloring agent in the coloring layer, there is a problem that it is difficult to make the coloring layer thin. Moreover, it has been difficult to achieve sufficient heat resistance and brightness with the yellow lake pigments currently on the market.

  The present invention has been made in view of the above circumstances, and provides a colorant dispersion, a colorant, and a colored resin composition, which are excellent in heat resistance and capable of forming a colored layer having a higher luminance and a thinner thickness. With the goal. Another object of the present invention is to provide a color filter having a colored layer that is formed with the use of the colored resin composition and has a higher brightness and a thinner thickness, and a display device using the color filter.

The color material dispersion according to the present invention contains a color material, a dispersant, and a solvent.
The color material contains a salt forming color material of a yellow dye,
In the salt forming colorant of the yellow dye, when the yellow dye is cationic, the counter ion is a heteropolyacid anion, and when the yellow dye is anionic, the counter ion is a polymetal salt-derived cation. It is characterized by that.

The color material according to the present invention is a salt forming color material of a yellow dye,
When the yellow dye is cationic, the counter ion is a heteropolyacid anion, and when the yellow dye is anionic, the counter ion is a cation derived from a polymetal salt.

  The colored resin composition according to the present invention includes the color material dispersion according to the present invention and a binder component.

  The cured product according to the present invention is a cured product of the colored resin composition according to the present invention.

  The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product according to the present invention. To do.

  The display device according to the present invention includes the color filter according to the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in heat resistance, can provide the color material dispersion liquid, color material, and colored resin composition which can form the colored layer by which it was highly bright and made more thin. In addition, according to the present invention, it is possible to provide a color filter having a high-intensity and thinner colored layer formed using the colored resin composition, and a display device using the color filter.

FIG. 1 is a schematic view showing an example of the color filter of the present invention. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. FIG. 3 is a schematic view illustrating an example of the organic light emitting display device of the present invention.

Hereinafter, the color material dispersion, the colored resin composition, the color filter, and the display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.

I. Color material dispersion The color material dispersion according to the present invention contains a color material, a dispersant, and a solvent.
The color material contains a salt forming color material of a yellow dye,
In the salt forming colorant of the yellow dye, when the yellow dye is cationic, the counter ion is a heteropolyacid anion, and when the yellow dye is anionic, the counter ion is a polymetal salt-derived cation. It is characterized by that.

Further, the color material according to the present invention is a salt-forming color material of a yellow dye,
When the yellow dye is cationic, the counter ion is a heteropolyacid anion, and when the yellow dye is anionic, the counter ion is a cation derived from a polymetal salt.

Since the color material dispersion according to the present invention contains the color material according to the present invention, the color resin composition prepared using the color material dispersion has excellent heat resistance and high brightness. A colored layer having a thinner thickness can be formed.
The action of the color material dispersion according to the present invention to exhibit the above effects is estimated as follows.
In the color material dispersion according to the present invention, the specific salt-forming color material has a dye skeleton, so that the transmittance of the color material is high and it is possible to form a colored layer having a higher luminance than when a pigment is used. Further, since the specific salt-forming color material is insolubilized by counter ions, the heat resistance of the color material is improved, and therefore, fading due to high-temperature heating such as post-baking is suppressed. The colorant dispersion according to the present invention is further improved in heat resistance and coloring power because the specific salt-forming colorant uses a cation derived from a heteropolyacid anion or a polymetal salt as a counter ion. Is an improvement. In the state of salt formation with the specific counter ion, dissociation or decomposition of the salt is unlikely to occur, so the rake reaction is likely to proceed and the property is closer to that of a pigment. Presumed.
Moreover, the coloring material dispersion of the present invention can suppress the amount of the coloring material added to obtain a desired chromaticity because the coloring power of the specific salt-forming coloring material is high. As a result, since the solid content of the entire colored layer can be reduced, by using the color material dispersion of the present invention, the luminance is further increased and a thinner colored layer can be formed. In addition, when using the color material of the present invention, compared with the case of using a color material having a lower coloring power, the content ratio of the binder component can be increased by reducing the content ratio of the color material in the colored layer. When the curability is excellent and the binder component is photosensitive, a high-definition fine line pattern can be formed.

The color material dispersion according to the present invention contains at least a color material, a dispersant, and a solvent, and may further contain other components within a range not impairing the effects of the present invention. is there.
Hereinafter, each component of the colorant dispersion according to the present invention will be described in detail.

<Color material>
The color material dispersion according to the present invention contains a salt forming color material of a yellow dye. In the salt forming colorant of the yellow dye, when the yellow dye is cationic, the counter ion is a heteropolyacid anion, and when the yellow dye is anionic, the counter ion is a polymetal salt-derived cation. .

  The yellow dye in the present invention is a dye concentration in which the transmittance of a spectral transmission spectrum in a visible light region of 380 nm to 780 nm in a dye solution obtained by dissolving a dye in an organic solvent such as water or alcohol is 1% at 440 nm. Sometimes, it refers to a dye having a transmittance of 90% or more at 540 nm. The spectral transmission spectrum can be measured using a general spectrophotometer such as a spectrophotometer UV-2600 manufactured by Shimadzu Corporation.

A known cationic or anionic yellow dye can be used as the yellow dye, and is not particularly limited. In the following description, when color index names are described, when only color index names having different numbers are listed, only the numbers may be listed.
Examples of the yellow dye include C.I. I. Acid Yellow 36, C.I. I. Azo dyes such as Basic Yellow 15, 19, 24, 25, 28, 29, 38, 39, 49, 51, 52, 53, 57, 62, 773; Solvent Yellow 33, 98, 157, Disperse Yellow 54, Quinoline dyes such as 160; I. Quinophthalone dyes such as Acid Yellow 3; I. C. Coumarin dyes such as Basic Yellow 40 and Solvent Yellow 160: 1; I. Cyanine dyes such as Basic Yellow 11, 13, 1-ethyl-3,3-dimethyl-2- (2- (phenylamino) -vinyl) -3H-indole-1-ium-5-sulfonate; I. Azine-based dyes such as basic yellow 14; I. Auramine dyes such as basic yellow 2, 3, 37; I. Acridine dyes such as basic yellow 5, 6, 7, 9; CI basic yellow 1, CI acid yellow 186, CI direct yellow 7, 8, 9, 14, 17, 18, 22 , 28, 29, 30, 54, 59, 165, etc .; I. Acid Yellow 1, C.I. I. Nitro dyes such as Disperse Yellow 42; methine dyes such as Disperse Yellow 201; and the like. Examples of coumarin dyes include those described in JP-A-2015-91947.
As the yellow dye, it is preferable that it contains one kind of skeleton selected from the group consisting of an azo skeleton, a quinoline skeleton, a quinophthalone skeleton, a coumarin skeleton, and a cyanine skeleton from the viewpoint of high effect of improving heat resistance. It is preferable from the viewpoint of heat resistance and luminance that it contains one kind of skeleton selected from the group consisting of a coumarin skeleton, a cyanine skeleton, and a quinophthalone skeleton. It is more preferable because it is easy.

Examples of the heteropolyacid anion used in the present invention include a heteropolyacid anion represented by an ionic formula (X ₁ M _m O _n ) ^c- . The heteropolyacid anion has a high compound density and can be used as a counter anion to improve the coloring power of the salt-forming colorant.
In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of poly atoms, and n represents a composition ratio of oxygen atoms. Examples of the poly atom M include Mo, W, V, Ti, and Nb. Examples of the hetero atom X include Si, P, As, S, Fe, and Co.
Among them, a heteropolyacid anion containing at least one of tungsten (W) and molybdenum (Mo) is preferable from the viewpoint of high brightness, excellent heat resistance and light resistance, high compound density, and improved coloring power. More preferred is a heteropolyacid containing P). Specific examples of preferred heteropolyacids include, for example, phosphotungstate ion [PW ₁₂ O ₄₀ ] ³⁻ , [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , silicotungstate ion [SiW ₁₂ O ₄₀ ] ⁴⁻ , phosphomolybdenum. Acid ion [PMo ₁₂ O ₄₀ ] ³⁻ , silicomolybdate ion [SiMo ₁₂ O ₄₀ ] ⁴⁻ , phosphotungsto molybdate ion [PW _12-x Mo _x O ₄₀ ] ³⁻ (x is an integer from 1 to 11) ), [P ₂ W _18-y Mo _y O ₆₂ ] ^6- (y is an integer from 1 to 17), and catalyst molybdate ion [SiW _12-x Mo _x O ₄₀ ] ⁴⁻ (x is from 1 to 11) And the following integers). Furthermore, it is heat resistant to be any one of phosphotungsto molybdate ion [PW ₁₀ Mo ₂ O ₄₀ ] ³⁻ , [PW ₁₁ Mo ₁ O ₄₀ ] ³⁻ , and phosphotungstate ion [PW ₁₂ O ₄₀ ] ³⁻ . From the viewpoint of properties, phosphotungstate ion [PW ₁₂ O ₄₀ ] ^3- is particularly preferable.

  Examples of the cation derived from the polymetal salt used in the present invention include a cation derived from a polymetal salt of a polyvalent metal that stably contains a polynuclear condensed ion as an active ingredient in an aqueous solution. Specific examples of the salt include polyaluminum chloride, zirconium oxychloride, polyaluminum sulfate aluminum silicate, and hydrates thereof. Among them, from the viewpoint of luminance and coloring power, polyaluminum chloride and oxychloride are exemplified. Zirconium is preferred, and polyaluminum chloride is more preferred.

As polyaluminum chloride, what is represented by following formula (1) is mentioned, for example.
Formula (1): Al _{n ′} (OH) _{m ′} Cl _{(3n′−m ′)}
(In Formula (1), n ′ is an integer of 2 to 20, and m ′ is an integer of (n ′ / 2) to (3n′−1).)

  In the formula (1), n ′ is preferably an integer of 2 to 10, and m ′ is preferably an integer of 2n ′ to (3n′−1). When n ′ is an odd number, the lower limit of m ′ is {(n ′ + 1) / 2} which is the smallest integer within the above range.

Preferable specific examples of the polyaluminum chloride include, for example, Al ₂ (OH) ₅ Cl, Al ₄ (OH) ₉ Cl _{3 and the} like.

  Moreover, as a commercial item of polyaluminum chloride, for example, trade names Takibaine # 1500, # 3000, PX # 1000, Tan White, manufactured by Taki Chemical Co., Ltd., trade names Paho, (trade name) manufactured by Asada Chemical Co., Ltd. ) Riken Green's brand name Purachem WT and the like.

  Examples of commercially available zirconium oxychloride include Zircozole ZC and Zircozole ZC-20 manufactured by Daiichi Rare Element Chemical Co., Ltd.

In addition, the counter ion used in the present invention has a molecular weight of preferably 7000 or less, more preferably 5000 or less, and further 4000 or less from the viewpoint that the coloring power can be improved and the colored layer can be made thinner. Is more preferable. The lower limit of the molecular weight of the counter ion is not particularly limited, but can be, for example, 50 or more.
Among these, the molecular weight of the polymetal salt used in the present invention is preferably 1000 or less, and more preferably 500 or less, from the viewpoint of improving the coloring power and further reducing the thickness of the colored layer.

The salt forming color material of the yellow dye is obtained by introducing a counter ion into the yellow dye to form a salt, and the salt formation can be performed by a conventionally known method.
In addition, the said salt-forming color material of the yellow dye may be used individually by 1 type, and may mix and use 2 or more types.

  In the color material dispersion of the present invention, the content ratio of the salt forming color material of the yellow dye contained in the entire color material is appropriately adjusted in order to achieve a desired chromaticity, and is not particularly limited. And from the point of brightness | luminance, it is preferable that it is 30 mass% or more, and it is more preferable that it is 50 mass% or more.

(Other color materials)
In the present invention, in addition to the above-described salt forming colorant of the yellow dye, in order to achieve the necessary chromaticity as long as the effects of the present invention are not impaired, other colorants are further contained. May be. Other colorants are not particularly limited and include various organic pigments, inorganic pigments and dispersible dyes. Among them, organic pigments and dispersible dyes are preferable, and organic pigments are more preferable.
Examples of the color material that is preferably used in combination with the salt forming color material of the yellow dye include a red color material, a green color material, and a yellow color material different from the salt formation color material of the yellow dye.

Examples of the organic pigment used as the other color material include those having the following color index (CI) numbers.
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279; I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 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, 61: 1, 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, 133, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 17 , 174,175,176,177,179,180,181,182,183,185,187,188,191,193,194,199,206,209: 1,212,213,214; C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73; C. I. Pigment Green 7, 10, 36, 37, 58, 59.
Among the organic pigments combined with the salt forming colorant of the yellow dye, C.I. I. At least one selected from the group consisting of CI Pigment Green 58 and 59 is preferable.

The dispersible dye is a dispersible dye different from the salt forming colorant of the yellow dye according to the present invention, and can be dispersed by imparting various substituents to the dye and making it insoluble in a solvent. And dyes that have become dispersible when used in combination with a solvent having low solubility, and rake colorants obtained by insolubilizing (raking) a dye that is soluble in the solvent with salt ions. By using a combination of such a dispersible dye and a dispersant, the dispersibility and dispersion stability of the dye can be improved.
As a guide, if the amount of dye dissolved in 10 g of solvent (or mixed solvent) is 20 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).
The dispersible dye can be appropriately selected from conventionally known dyes and is not particularly limited. For example, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, And phthalocyanine dyes.

  When the color material dispersion of the present invention contains other color materials other than the salt forming color material of the yellow dye, the content of the other color materials may be 70% by mass or less of the entire color material. Preferably, it is 50 mass% or less.

<Dispersant>
As the dispersant, a known dispersant can be appropriately selected and used. For example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed.

  Examples of the polymer dispersant include polymer dispersants such as modified polyurethane, modified polyacrylate, modified polyester, and modified polyamide. Specifically, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (partial) ammonium Salts (partial) alkylamine salts; (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters having amino groups, (partial) acid-modified products of amino groups of the polymers; hydroxyl group-containing polyacrylic acid (Co) polymers of hydroxyl-containing unsaturated carboxylic acid esters such as esters and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; poly (lower alkylene imines) and free Examples thereof include amides obtained by reaction with carboxy group-containing polyesters and salts thereof.

The dispersant used in the present invention is preferably a dispersant having an amine value from the viewpoint that the colorant can be suitably dispersed and the dispersion stability is good.
Among these, as the dispersant having an amine value, a polymer dispersant is preferable, a polymer dispersant containing a nitrogen atom in the main chain or side chain is more preferable, and a polymer dispersant having an amine or ammonium salt is more preferable. When the polymer dispersant having an amine or ammonium salt is used, the amine or ammonium salt is preferably present in the side chain or the resin terminal.
Examples of the polymer dispersant having an amine or ammonium salt include (partial) amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid; Polyurethanes; unsaturated polyamides; polyethyleneimine derivatives; polyallylamine derivatives and the like.

  In the present invention, commercially available products used as a dispersant include, for example, EFKA-4046, EFKA-4047, EFKA polymer 10, EFKA polymer 400, EFKA polymer 401, EFKA polymer 4300, EFKA polymer 4310, EFKA polymer 4320, and EFKA polymer. 4330 (above, manufactured by BASF Japan), Disperbyk111, Disperbyk161, Disperbyk165, Disperbyk167, Disperbyk182, Disperbyk2000, Disperbyk2001, BYK-LPN6919, BYK-LPN6919, BYK-LPN6919, BYK-LPN6919, BYK-LPN6919, BYK-LPN6919, BYK-LPN6919 000 (manufactured by Lubrizol Corporation), Ajisper (registered trademark) PB821, PB822 (manufactured by Ajinomoto Fine-Techno Co.), and the like.

  In addition, as a dispersant used to disperse the coloring material, among them, a polymer dispersant composed of a polymer containing a repeating unit having a tertiary amine can achieve excellent luminance with excellent dispersibility, The formation of a colored layer is preferred because it can suppress the generation of foreign matter, has excellent re-solubility in a solvent, and can form a colored layer with excellent heat resistance.

(Polymer including repeating unit having tertiary amine)
Examples of the polymer containing a repeating unit having a tertiary amine include (a) a block copolymer having a block part composed of a repeating unit having a tertiary amine and a block part having a solvent affinity, and (b) 3 A graft copolymer containing a repeating unit having a secondary amine and a repeating unit having a polymer chain having solvent affinity is preferably used. In the graft copolymer, the repeating unit having a tertiary amine may be contained in a polymer chain corresponding to a branch part, and the solvent affinity with the repeating unit having a polymer chain containing a repeating unit having a tertiary amine It may be a graft copolymer containing a repeating unit having a polymer chain.

The repeating unit having a tertiary amine only needs to have a tertiary amine, and the tertiary amine may be contained in the side chain of the block polymer or may constitute the main chain.
Among them, a repeating unit having a tertiary amine in the side chain is preferable, and among them, the structure represented by the following general formula (I) is preferable because the main chain skeleton is hardly thermally decomposed and has high heat resistance. Is more preferable.

（一般式（Ｉ）中、Ｒ^１１は、水素原子又はメチル基、Ｑは、直接結合又は２価の連結基、Ｒ^１２は、炭素数１〜８のアルキレン基、−［ＣＨ（Ｒ^１５）−ＣＨ（Ｒ^１６）−Ｏ］_ｘ−ＣＨ（Ｒ^１５）−ＣＨ（Ｒ^１６）−又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−（ＣＨ_２）_ｙ−で示される２価の有機基、Ｒ^１３及びＲ^１４は、それぞれ独立に、置換されていてもよい鎖状又は環状の炭化水素基を表すか、Ｒ^１３及びＲ^１４が互いに結合して環状構造を形成する。Ｒ^１５及びＲ^１６は、それぞれ独立に水素原子又はメチル基である。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。）

(In General Formula (I), R ¹¹ is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, R ¹² is an alkylene group having 1 to 8 carbon atoms, — [CH (R ¹⁵ ) _{^{-CH (R 16) -O] x}} -CH (R 15) -CH (R 16) - or _{- [(CH 2) y -O} ] z - (CH 2) y - 2 monovalent organic group represented by , ^{R 13} and ^{R 14} each independently represent a optionally substituted linear or cyclic hydrocarbon ^{group, R 13} and ^{R 14} form a ring structure by bonding with each other ^{.R 15} and R ¹⁶ each independently represents a hydrogen atom or a methyl group.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

  Examples of the divalent linking group Q in the general formula (I) include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (- R′—OR ″ —: R ′ and R ″ each independently represents an alkylene group) and combinations thereof. Among these, Q is a —COO— group or —CONH— from the viewpoint of heat resistance of the polymer obtained, solubility in propylene glycol monomethyl ether acetate (PGMEA) suitably used as a solvent, and a relatively inexpensive material. It is preferably a group.

Divalent organic group ^{R 12} in the general formula (I) is an alkylene group having 1 to 8 carbon ^{atoms, - [CH (R 15)} -CH (R 16) -O] x -CH (R 15) -CH (R ¹⁶ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y —. The alkylene group having 1 to 8 carbon atoms may be linear or branched.
R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group.
R ¹² is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility. Among them, R ¹² is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. Groups are more preferred.

Examples of the optionally substituted chain or cyclic hydrocarbon group in R ¹³ and R ¹⁴ include an alkyl group, an aralkyl group, and an aryl group.
1-18 are preferable and, as for the carbon atom number of an alkyl group, it is more preferable that they are a methyl group or an ethyl group especially.
7-20 are preferable and, as for the carbon atom number of an aralkyl group, 7-14 are more preferable.
Moreover, 6-24 are preferable and, as for the carbon atom number of an aryl group, 6-12 are more preferable. The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.
Moreover, the hydrogen atom in a hydrocarbon group may be substituted by halogen atoms, such as a C1-C5 alkyl group, a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the cyclic structure formed by combining R ¹³ and R ^{14 in} the general formula (I) include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. It is done. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring.

  Examples of the repeating unit represented by the general formula (I) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and other alkyl group-substituted amino groups. Examples include group-containing (meth) acrylates, alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and the like. Of these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.

  In the block part containing a repeating unit having a tertiary amine, it is preferable that three or more structural units represented by the general formula (I) are included. Especially, from the point which improves a dispersibility and dispersion stability, it is preferable to contain 3-100 pieces, It is more preferable to contain 3-50 pieces, Furthermore, it is more preferable to contain 3-30 pieces.

A block having a block part (hereinafter sometimes referred to as A block) containing a repeating unit having a tertiary amine and a block part having solvent affinity (hereinafter sometimes referred to as B block). In the copolymer, the block portion having solvent affinity does not have the structural unit represented by the general formula (I) from the viewpoint of improving solvent affinity and improving dispersibility. It has a solvent affinity block part having a structural unit copolymerizable with (I). In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like can be used. Among these, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.
The structural unit copolymerizable with the general formula (I) is a structural unit represented by the following general formula (II) from the viewpoint of improving heat resistance while improving dispersibility and dispersion stability of the coloring material. It is preferable that

（一般式（ＩＩ）中、Ｒ^１７は、水素原子又はメチル基、Ａは、直接結合又は２価の連結基、Ｒ^１８は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^１９）−ＣＨ（Ｒ^２０）−Ｏ］_ｘ−Ｒ^２１又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^２１で示される１価の基である。Ｒ^１９及びＲ^２０は、それぞれ独立に水素原子又はメチル基であり、Ｒ^２１は、水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、又は−ＣＨ_２ＣＯＯＲ^２２で示される１価の基であり、Ｒ^２２は水素原子又は炭素数１〜５の直鎖状、分岐状、又は環状のアルキル基である。ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。）

(In General Formula (II), R ¹⁷ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, R ¹⁸ is an alkyl group having 1 to 18 carbon atoms, and an alkenyl group having 2 to 18 carbon atoms. Group, an aralkyl group, an aryl group, a monovalent group represented by — [CH (R ¹⁹ ) —CH (R ²⁰ ) —O] _x —R ²¹ or — [(CH ₂ ) _y —O] _z —R ²¹ R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a methyl group, and R ²¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, A monovalent group represented by an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ²² , wherein R ²² is a hydrogen atom or a linear, branched, or cyclic alkyl having 1 to 5 carbon atoms. X is an integer from 1 to 18, and y is from 1 to 5. Integer, z represents an integer of 1 to 18.)

  The divalent linking group A of the general formula (II) can be the same as Q in the general formula (I), and propylene glycol which is suitably used as the heat resistance and solvent of the obtained polymer. From the viewpoint of solubility in monomethyl ether acetate (PGMEA) and a relatively inexpensive material, A is preferably a —COO— group.

In R ¹⁸ , the alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl group, Examples thereof include a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, and a lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic.
Among these, R ¹⁸ is preferably a methyl group, various butyl groups, various hexyl groups, benzyl group, cyclohexyl group, or hydroxyethyl group from the viewpoint of dispersibility and substrate adhesion.

Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. 6-24 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. 7-20 are preferable and, as for carbon number of an aralkyl group, 7-14 are more preferable.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include an alkenyl group, a nitro group, and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.

In the monovalent group represented by R ²¹ , examples of the substituent that may be included include linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms, F, Cl, Br and the like. A halogen atom etc. can be mentioned.
The alkyl group, and alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group having 1 to 18 carbon atoms of ^{R 21} may be the same as the ^{R 18.}
In the above R ¹⁸ , x, y and z are the same as R ¹² in the general formula (I).

  What is necessary is just to adjust suitably the number of the structural units which comprise a solvent affinity block part in the range which a color material dispersibility improves. Among them, the number of structural units constituting the solvent-affinity block part is 10 or more and 200 or less from the viewpoint that the solvent-affinity part and the colorant affinity part act effectively and improve the dispersibility of the colorant. Preferably, it is 10 or more and 100 or less, more preferably 10 or more and 70 or less.

The solvent-affinity block part may be selected so as to function as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block part may contain one kind or two kinds. The above repeating unit may be included.
In the block copolymer used as the dispersant of the present invention, the ratio between the number m of the structural unit represented by the general formula (I) and the number n of other structural units constituting the solvent-affinity block unit m / n is preferably in the range of 0.01 to 1 and more preferably in the range of 0.05 to 0.7 from the viewpoint of the dispersibility and dispersion stability of the color material. preferable.

Further, among them, in the present invention, the dispersant is a polymer having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less that includes the structure represented by the general formula (I), and has good dispersibility. It is preferable from the viewpoint of improving luminance and contrast without depositing foreign matters.
When the amine value is within the above range, it is excellent in viscosity stability over time and heat resistance, and also in alkali developability and solvent resolubility. In the present invention, the amine value of the dispersant is preferably 80 mgKOH / g or more, more preferably 90 mgKOH / g or more, from the viewpoint of dispersibility and dispersion stability. On the other hand, from the viewpoint of solvent resolubility, the amine value of the dispersant is preferably 110 mgKOH / g or less, more preferably 105 mgKOH / g or less.
The amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of a sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if it is an amino group that forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant is itself The amine value of can be measured.

The acid value of the dispersant used in the present invention is not particularly limited, but in particular, it is preferably 18 mgKOH / g or less, more preferably 12 mgKOH / g or less, from the viewpoint of improving development adhesion and solvent resolubility. More preferably. On the other hand, the acid value of the dispersant used in the present invention is preferably 0 mgKOH / g from the viewpoint of further improving the solvent re-solubility and development adhesion, and from the viewpoint of substrate adhesion and dispersion stability. The smaller the acid value, the less likely it is to be eroded by the basic developer, which is considered to improve the development adhesion. On the other hand, from the viewpoint of the effect of suppressing the development residue, it is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more.
In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, from the viewpoint of good development adhesion and solvent resolubility, 12 mgKOH / g More preferably, it is g or less. Further, the acid value of the block copolymer before salt formation is preferably 0 mgKOH / g from the viewpoint of further improving the solvent re-solubility and development adhesion, and from the viewpoint of substrate adhesion and dispersion stability. On the other hand, from the viewpoint of the effect of suppressing the development residue, it is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more.

  When the colorant concentration is increased and the dispersant content is increased, the binder amount is relatively decreased. Therefore, when the colored resin layer is developed, it becomes easy to peel from the base substrate during development. When the dispersant contains a B block containing a structural unit derived from a carboxy group-containing monomer and has the specific acid value, the development adhesion is improved. If the acid value is too high, the developability is excellent, but it is presumed that the polarity is too high and peeling easily occurs during development.

  In the present invention, the dispersant is a polymer having a structure represented by the general formula (I) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less, and an acid value of 0 mgKOH / g or more and 18 mgKOH. / G or less and having a glass transition temperature of 30 ° C. or more is excellent in colorant dispersion stability and improves contrast, and when used as a colored resin composition, it has excellent solvent resolubility, and further high development. It is preferable from the point which has adhesiveness.

  As the carboxy group-containing monomer, a monomer that can be copolymerized with a monomer that derives the structural unit represented by the general formula (I) and contains an unsaturated double bond and a carboxy group can be used. Examples of such a monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, acrylic acid dimer, and the like. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use acid anhydride group containing monomers, such as maleic anhydride and itaconic anhydride, as a precursor of a carboxy group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxy group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the range of the specific acid value. Although it is not limited, it is preferable that it is 0.05 mass% or more and 4.5 mass% or less with respect to the total mass of all the structural units of a block copolymer, and is 0.07 mass% or more and 3.7 mass% or less. More preferably.
Since the content ratio of the structural unit derived from the carboxy group-containing monomer is not less than the lower limit value, the effect of suppressing the development residue is expressed, and since it is not more than the upper limit value, the development adhesiveness is deteriorated and the solvent resolubility is reduced. Deterioration can be prevented.
In addition, the structural unit derived from a carboxy group-containing monomer may have a desired acid value, and may be composed of one kind or may contain two or more kinds of structural units.

  In the block copolymer, the ratio m / n of the unit number m of the structural unit of the A block and the unit number n of the structural unit of the B block is in the range of 0.05 to 1.5. In view of the dispersibility and dispersion stability of the coloring material, it is more preferably within the range of 0.1 to 1.0.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 or more and 20000 or less, and preferably 2000 or more and 15000 or less, from the viewpoint of improving the colorant dispersibility and dispersion stability. More preferably, it is more preferably 3000 or more and 12000 or less.
Here, the weight average molecular weight is determined as a standard polystyrene conversion value by (Mw) and gel permeation chromatography (GPC). The macromonomer, salt-type block copolymer, and graft copolymer that are the raw materials for the block copolymer are also subjected to the above conditions.

  The manufacturing method of the said block copolymer is not specifically limited. Although a block copolymer can be produced by a known method, it is preferable to produce it by a living polymerization method.

  Specific examples of the block copolymer having a block part containing a repeating unit having a tertiary amine and a block part having a solvent affinity include, for example, a block copolymer described in Japanese Patent No. 4911253 Can be mentioned as suitable.

In the present invention, from the viewpoint of dispersibility and dispersion stability of the coloring material, at least a part of the amino group in the polymer containing the repeating unit having the tertiary amine, an organic acid compound, and a halogenated hydrocarbon. It is also preferable to use a salt forming a salt as a dispersant (hereinafter, such a polymer may be referred to as a salt-type polymer).
Among them, the polymer containing a repeating unit having a tertiary amine is a block copolymer, and the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. And preferred from the viewpoint of excellent dispersion stability. Specific examples of the organic acid compound used for such a dispersant include organic acid compounds described in JP 2012-236882 A and the like.
The halogenated hydrocarbon is preferably at least one of allyl halides such as allyl bromide and benzyl chloride and aralkyl halides from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

The said dispersing agent may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, when each color material dispersion is prepared using a different dispersant for each color material, a different dispersant may be used.
The content in the case of using the dispersant is not particularly limited as long as it can uniformly disperse the color material. For example, the content is based on the total solid content of the color resin composition for color filters. It can be used at 1% by mass to 40% by mass. Furthermore, it is preferable to mix | blend in 2 mass%-30 mass%, and it is preferable to mix | blend especially in the ratio of 3 mass%-25 mass%. If it is more than the said lower limit, it is excellent in the dispersibility and dispersion stability of a color material, and is excellent in the storage stability of the colored resin composition for color filters. Moreover, if it is below the said upper limit, developability will become favorable. In particular, when a colored layer having a high colorant concentration is formed, the content of the dispersant is 2% by mass to 25% by mass, more preferably 3% by mass with respect to the total solid content of the color resin composition for color filters. It is preferable to mix | blend in the ratio of% -20 mass%.

<Solvent>
The solvent is not particularly limited as long as it does not react with each component in the colorant dispersion and can dissolve or disperse them.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Tone solvents; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxy Carbitol acetate solvents such as ethoxyethyl acetate, carbitol acetate, butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol mono Glycol ether solvents such as chill ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactone solvents such as butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; Examples thereof include organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, carbitol acetate, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate It is preferable that it is 1 or more types selected from the group which consists of ethyl lactate and 3-methoxybutyl acetate from the point of the solubility of another component, and the applicability | paintability.

  The solid content in the colorant dispersion containing the solvent is such that the solid content is 0.1 parts by mass or more and 70 parts by mass or less when the total colorant dispersion containing the solvent is 100 parts by mass. It is more preferable that it is 1.0 part by mass or more and 50 parts by mass or less.

<Other ingredients>
As long as the effect of this invention is not impaired, you may mix | blend a dispersion | distribution auxiliary resin and another component with the coloring material dispersion liquid which concerns on this invention as needed.
Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified by a colored resin composition described later. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, and may have the effect of stabilizing the dispersion or reducing the dispersant due to the dispersion stabilizing effect.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

  The color material dispersion according to the present invention can be used as a preliminary preparation for preparing a colored resin composition to be described later, (color material component mass in the composition) / (other than the color material component in the composition). Is a colorant dispersion having a high solid content mass ratio. Specifically, the ratio is usually 1.0 or more. By mixing the colorant dispersion and each component described later, a colored resin composition having excellent dispersibility can be prepared.

<Method for producing colorant dispersion>
The colorant dispersion of the present invention can be obtained by adding at least the salt forming colorant of the yellow dye and the dispersant to the solvent and performing a conventionally known dispersion treatment. Examples of the disperser for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as ball mills and vibration ball mills, bead mills such as paint conditioners, continuous disk type bead mills, and continuous annular type bead mills. . As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, and more preferably 0.05 to 1.0 mm.

  The average dispersed particle diameter of the color material in the color material dispersion liquid varies depending on the type of the color material used, but is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. The average dispersed particle size of the color material in the color material dispersion is the dispersed particle size of the color material particles dispersed in the color material dispersion containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. Is. For particle size measurement with a laser light scattering particle size distribution meter, the color material dispersion is appropriately diluted to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times). Etc.) and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is a volume average particle size.

II. Colored resin composition The colored resin composition according to the present invention comprises the colorant dispersion according to the present invention and a binder component.

  The colored resin composition according to the present invention can form a colored layer that is excellent in heat resistance, has high brightness, and is made thinner by containing the above-described colorant dispersion according to the present invention.

  The colored resin composition of the present invention contains at least the colorant dispersion according to the present invention and a binder component, and may further contain other components as long as the effects of the present invention are not impaired. It ’s good. Since the colorant dispersion according to the present invention is as described above, the binder component included in the colored resin composition of the present invention and the optional additive component that may be further included will be described below.

<Binder component>
The colored resin composition of the present invention contains a binder component in order to impart film formability and adhesion to the surface to be coated. In order to impart sufficient hardness to the coating film, it is preferable to contain a curable binder component. It does not specifically limit as a curable binder component, The curable binder component used in forming the coloring layer of a conventionally well-known color filter can be used suitably.
Examples of the curable binder component include a photocurable binder component containing a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, and the like, and a thermosetting resin that can be polymerized and cured by heating. What contains the thermosetting binder component to contain can be used.

When using a photolithography process when forming a colored layer, the photosensitive binder component which has alkali developability is used suitably. In addition, you may further use a thermosetting binder component for the photosensitive binder component.
Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. Examples of the positive photosensitive binder component include a system containing an alkali-soluble resin and an o-quinonediazide group-containing compound as a photosensitizing component.

On the other hand, as the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used.
In the colored resin composition according to the present invention, a negative photosensitive binder component is preferable from the viewpoint that a pattern can be easily formed by a photolithography method using an existing process.
Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator constituting the negative photosensitive binder component will be specifically described.

(Alkali-soluble resin)
The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected from those that act as a binder resin and are soluble in an alkali developer used for pattern formation.
In the present invention, the alkali-soluble resin can be based on an acid value of 40 mgKOH / g or more.
A preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group. Specifically, acrylic resins such as an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group are used. And epoxy (meth) acrylate resins having a carboxy group. Among these, particularly preferred are those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Moreover, acrylic resins such as these acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination of two or more.

An acrylic resin such as an acrylic copolymer having a constitutional unit having a carboxy group and a styrene-acrylic copolymer having a carboxy group includes, for example, a carboxy group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co) polymer obtained by (co) polymerizing other polymerizable monomers by a known method.
As the carboxy group-containing ethylenically unsaturated monomer, those similar to the carboxy group-containing ethylenically unsaturated monomer described in the section of the dispersant can be used. Among them, copolymerization, cost, solubility, glass (Meth) acrylic acid is particularly preferred from the viewpoint of transition temperature and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring that is a bulky group in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is eased, and substrate adhesion is improved. Moreover, solvent resistance, especially swelling of the colored layer is suppressed. Although the action is unclear, the bulky hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer, resulting in an increase in the strength of the coating and suppression of swelling by the solvent. It is estimated that.
Examples of such hydrocarbon rings include aliphatic hydrocarbon rings that may have a substituent, aromatic hydrocarbon rings that may have a substituent, and combinations thereof. May have a substituent such as an alkyl group, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, or a halogen atom.
The hydrocarbon ring may be contained as a monovalent group or a divalent or higher group.

When an aliphatic hydrocarbon ring is included as the hydrocarbon ring, it is preferable from the viewpoint of improving the heat resistance and adhesion of the colored layer and improving the luminance of the obtained colored layer.
Moreover, when the said cardo structure is included, the sclerosis | hardenability of a colored layer improves and it is especially preferable from the point which improves solvent resistance (NMP swelling suppression).

The alkali-soluble resin preferably has a bridged cyclic hydrocarbon ring, which is an aliphatic hydrocarbon ring having a structure in which two or more rings share two or more atoms.
Specific examples of the bridged cyclic hydrocarbon ring include norbornane, isobornane, adamantane, tricyclo [5.2.1.0 (2,6)] decane, tricyclo [5.2.1.0 (2,6)]. Decene, tricyclopentene, tricyclopentane, tricyclopentadiene, dicyclopentadiene; groups in which a part of these groups are substituted with a substituent are mentioned.
Examples of the substituent include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a halogen atom.

  The lower limit of the number of carbon atoms in the crosslinked cyclic hydrocarbon ring is preferably 5 or more, and particularly preferably 7 or more, from the viewpoint of compatibility with other materials and solubility in an alkaline developer. The upper limit is preferably 12 or less, and particularly preferably 10 or less.

The acrylic copolymer having a structural unit having a carboxy group and the hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned “other monomer capable of copolymerization”. be able to.
Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl. (Meth) acrylate, styrene, etc. are mentioned. From the point that the cross-sectional shape of the colored layer after development has a large effect of being maintained in the heat treatment, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl ( It is preferable to use at least one selected from (meth) acrylate, benzyl (meth) acrylate, and styrene.

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in the side chain. In the case of having an ethylenic double bond, the alkali-soluble resins, or the alkali-soluble resin and the polyfunctional monomer can form a cross-linked bond in the curing step of the resin composition at the time of producing the color filter. The film strength of the cured film is further improved and the development resistance is improved, and the thermal contraction of the cured film is suppressed and the adhesiveness with the substrate is excellent.
The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of introducing an ethylenic double bond into a side chain by adding a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, to the carboxy group of the alkali-soluble resin Or by introducing a structural unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an ethylenic double bond in the molecule, and introducing an ethylenic double bond into the side chain. Etc.

  The alkali-soluble resin of the present invention may further contain other structural units such as a structural unit having an ester group such as methyl (meth) acrylate and ethyl (meth) acrylate. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the colored resin composition, but also functions as a component that improves the solubility in a solvent and further the solvent re-solubility.

  The alkali-soluble resin in the present invention is preferably an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxy group and a structural unit having a hydrocarbon ring, It is an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxy group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond. Is more preferable.

  The alkali-soluble resin can be made into an alkali-soluble resin having desired performance by appropriately adjusting the charged amount of each structural unit.

The charging amount of the carboxy group-containing ethylenically unsaturated monomer is preferably 5% by mass or more and more preferably 10% by mass or more with respect to the total amount of the monomer from the viewpoint of obtaining a good pattern. On the other hand, from the viewpoint of suppressing film roughness on the pattern surface after development, the amount of the carboxy group-containing ethylenically unsaturated monomer is preferably 50% by mass or less, and 40% by mass or less, based on the total amount of monomers. More preferably.
The solubility of the coating film obtained when the ratio of the carboxy group-containing ethylenically unsaturated monomer is not less than the above lower limit is sufficient for the alkali developer, and the ratio of the carboxy group-containing ethylenically unsaturated monomer is the above upper limit. When it is below, there is a tendency that the formed pattern is not easily detached from the substrate and the pattern surface is not easily roughened during development with an alkali developer.

  The compound having both an epoxy group and an ethylenic double bond is preferably 10% by mass or more and 95% by mass or less, and 15% by mass or more and 90% by mass with respect to the charged amount of the carboxy group-containing ethylenically unsaturated monomer. % Or less is more preferable.

The weight average molecular weight (Mw) of the carboxy group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If it is less than 1,000, the binder function after curing may be remarkably lowered. If it exceeds 50,000, pattern formation may be difficult during development with an alkali developer.
In addition, the said weight average molecular weight (Mw) of a carboxy-group containing copolymer can be measured by Shodex GPC system-21H (polystyrene) as a standard substance and THF as an eluent (Shodex GPC System-21H).

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxy group, Epoxy (meth) obtained by making the reaction product of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones. The epoxy (meth) acrylate resin having a carboxy group may be used alone or in combination of two or more.

As the alkali-soluble resin, it is preferable to select and use an acid-soluble resin having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) with respect to an alkaline aqueous solution used for the developer. The alkali-soluble resin preferably has an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for the developer and adhesion to the substrate. It is preferable that it is 80 mgKOH / g or more and 280 mgKOH / g or less.
In the present invention, the acid value can be measured according to JIS K 0070: 1992.

The ethylenically unsaturated bond equivalent in the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group improves the film strength of the cured film, improves the development resistance, and obtains the effect of excellent adhesion to the substrate. From the viewpoint, it is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Moreover, since the ratio of other structural units, such as the structural unit which has the said carboxy group, and the structural unit which has a hydrocarbon ring, can be relatively increased if it is 100 or more, it is excellent in developability and heat resistance. Yes.
Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

Formula (1)
Ethylenically unsaturated bond equivalent (g / mol) = W (g) / M (mol)
(In Formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)

  The ethylenically unsaturated bond equivalent is determined, for example, by measuring the number of ethylenic double bonds contained in 1 g of alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070: 1992. It may be calculated.

  The alkali-soluble resin used in the colored resin composition may be used singly or in combination of two or more, and the content is not particularly limited, but the solid of the colored resin composition The alkali-soluble resin is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less, based on the total amount of the components. When the content of the alkali-soluble resin is not less than the above lower limit, sufficient alkali developability can be easily obtained, and when the content of the alkali-soluble resin is not more than the above upper limit, film roughness or lack of pattern can be caused during development. It is easy to suppress.

(Polyfunctional monomer)
The polyfunctional monomer used in the colored resin composition is not particularly limited as long as it can be polymerized by a photoinitiator described later, and usually a compound having two or more ethylenically unsaturated double bonds is preferable. In particular, a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is preferable.
Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples thereof include those described in JP2013-029832A.

  These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. When the colored resin composition of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three (trifunctional) or more polymerizable double bonds. Preferred are poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid of dipentaerythritol penta (meth) acrylate Modified product, dipentaerythritol hexa Meth) acrylate are preferable.

  The content of the polyfunctional monomer used in the colored resin composition is not particularly limited, but the polyfunctional monomer is preferably 5% by mass or more and 60% by mass or less, more preferably based on the total solid content of the colored resin composition. Is in the range of 10 mass% or more and 40 mass% or less. When the content of the polyfunctional monomer is not less than the above lower limit, photocuring proceeds sufficiently, and the exposed portion can suppress elution during development, and when the content of the polyfunctional monomer is not more than the above upper limit, alkali development Sex is enough.

(Photoinitiator)
There is no restriction | limiting in particular as an initiator used in the colored resin composition of this invention, From the conventionally known various initiators, it can be used 1 type or in combination of 2 or more types.
Examples of the initiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-amino ketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, and the like. Can do. Specific examples of the initiator include aromatic ketones such as benzophenone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and benzoin such as ethylbenzoin. , Biimidazoles such as 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, and halo such as 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Methyloxadiazole compounds, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2 Morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4 -Benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- 4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1- For example, propanone.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1- Butanone, 4,4′-bis (diethylamino) benzophenone, and diethylthioxanthone are preferably used.

In the present invention, the initiator preferably contains an oxime ester photoinitiator from the viewpoint of improving sensitivity. As the oxime ester photoinitiator, those having an aromatic ring are preferable, and those having a condensed ring including an aromatic ring are more preferable from the viewpoint of reducing contamination of the colored resin composition due to decomposition products and contamination of the apparatus. Preferably, it has a condensed ring containing a benzene ring and a hetero ring.
As the oxime ester photoinitiator, 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), JP 2000-80068 A, JP 2001-233842 A, Special Table 2010-527339, Special Table 2010-527338, It can be appropriately selected from oxime ester photoinitiators described in JP2013-041153A and the like. As commercial products, Irgacure OXE-01 (manufactured by BASF) having a carbazole skeleton, Adeka Arcles NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials), ADEKA having a diphenyl sulfide skeleton ARCULS NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (manufactured by Changzhou Power Electronics New Materials), TR-PBG-365 (Changzhou Power Electronics New Materials, Inc.) having a fluorene skeleton May be used. In particular, it is preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of luminance. It is preferable to use an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.
Further, it is preferable to use two or more kinds of oxime ester photoinitiators in terms of easily improving luminance and development resistance and having a high effect of suppressing water stain generation. In particular, the combined use of two types of oxime ester photoinitiators having a diphenyl sulfide skeleton, or the combined use of an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having a fluorene skeleton is high in luminance and heat resistance. It is preferable from the point of high property. In addition, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton in combination with an oxime ester photoinitiator having a fluorene skeleton or an oxime ester photoinitiator having diphenyl sulfide in terms of excellent sensitivity and luminance.

  In addition, it is preferable to use a photoinitiator having a tertiary amine structure in combination with an oxime ester photoinitiator from the viewpoint of suppressing water stain and improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure that is an oxygen quencher in the molecule, radicals generated from the initiator are hardly deactivated by oxygen, and sensitivity can be improved. is there. As a commercial item of the photoinitiator having the tertiary amine structure, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, Irgacure 369, manufactured by BASF), 4,4′-bis (diethylamino) benzophenone (for example, High Cure ABP, Kawaguchi Pharmaceutical).

The content of the photoinitiator used in the colored resin composition of the present invention is usually about 0.01 parts by mass to 100 parts by mass, preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the polyfunctional monomer. Or less. If this content is not less than the above lower limit, the photocuring is sufficiently advanced and the exposed portion is prevented from being eluted during development, while if it is not more than the above upper limit, the yellowing of the resulting colored layer is weakened and the luminance is reduced. It can suppress that it falls.
Moreover, as a photoinitiator used in the colored resin composition of the present invention, the total content of the oxime ester photoinitiator is 0.1% by mass or more and 12.0% with respect to the total solid content of the colored resin composition. It is preferable from the viewpoint of sufficiently exhibiting the combined effect of these photoinitiators to be in the range of not more than mass%, more preferably not less than 1.0 mass% and not more than 8.0 mass%.

Moreover, when the said binder component contains a thermosetting resin, the colored resin composition of this invention may contain the thermal-polymerization initiator further as needed. There is no restriction | limiting in particular as a thermal-polymerization initiator, It uses it combining 1 type, or 2 or more types from various thermal-polymerization initiators, such as a conventionally known thermal radical polymerization initiator and a thermal cationic polymerization initiator. Can do.
Examples of the thermal radical polymerization initiator include azo compounds such as 2,2′-azobisbutyronitrile (AIBN), peroxides such as benzoyl peroxide (BPO), and the like. Examples of the thermal cationic polymerization initiator include benzenesulfonic acid esters and alkylsulfonium salts.
When the colored composition of the present invention contains a thermal polymerization initiator, the total content of various initiators relative to the total solid content of the colored resin composition is 0.1% by mass or more and 15.0% by mass or less. Preferably, it is 1.0 mass% or more and 10.0 mass% or less.

  The binder component used in the colored resin composition of the present invention preferably has a total content of 35% by mass to 97% by mass, and 40% by mass to 96% by mass with respect to the total solid content of the colored resin composition. It is more preferable to mix | blend in the following ratios. If it is more than the said lower limit, the colored layer excellent in hardness and the adhesiveness with a board | substrate can be obtained. Moreover, if it is below the said upper limit, it is excellent in developability and generation | occurrence | production of the fine wrinkles by heat shrink is also suppressed.

<Optional components>
The colored resin composition may contain various additives as necessary.
Examples of additives include, in addition to antioxidants, mercapto compounds, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters. Etc.

  Specific examples of the surfactant and the plasticizer include those described in JP2013-029832A.

<Combination ratio of each component in the colored resin composition>
The content of the color material is preferably 3% by mass or more and 65% by mass or less, more preferably 4% by mass or more and 60% by mass or less, based on the total solid content of the colored resin composition. If it is more than the said lower limit, the colored layer at the time of apply | coating the colored resin composition to predetermined | prescribed film thickness (usually 1.0-5.0 micrometers) has sufficient color density. Moreover, if it is below the said upper limit, while being excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. When a colored layer having a particularly high color material concentration is formed, the content of the color material is 15% by mass or more and 65% by mass or less, more preferably 25% by mass or more, based on the total solid content of the color resin composition. It is preferable to mix | blend in the ratio of 60 mass% or less.
Further, the content of the dispersant is not particularly limited as long as it can uniformly disperse the color material. For example, it is 1% by mass or more based on the total solid content of the colored resin composition. 40% by mass or less can be used. Furthermore, it is preferable to mix | blend in the ratio of 2 mass% or more and 30 mass% or less with respect to the solid content whole quantity of a coloring resin composition, and it is preferable to mix | blend especially in the ratio of 3 mass% or more and 25 mass% or less. If it is more than the said lower limit, it is excellent in the dispersibility and dispersion stability of a coloring material, and is excellent in the storage stability of a colored resin composition. Moreover, if it is below the said upper limit, developability will become favorable. When a colored layer having a particularly high colorant concentration is formed, the content of the dispersant is 2% by mass or more and 25% by mass or less, more preferably 3% by mass or more, based on the total solid content of the colored resin composition. It is preferable to mix | blend in the ratio of 20 mass% or less. In addition, the mass of a dispersing agent is a total mass of the said block copolymer before salt formation, an organic acid compound, etc. in the case of a salt type block copolymer.
Moreover, what is necessary is just to set content of a solvent suitably in the range which can form a colored layer accurately. Usually, it is preferably within the range of 55% by mass or more and 95% by mass or less, and particularly preferably within the range of 65% by mass or more and 88% by mass or less, with respect to the total amount of the colored resin composition containing the solvent. More preferred. When the content of the solvent is within the above range, the coating property can be excellent.

<Method for producing colored resin composition>
The method for producing the colored resin composition of the present invention is not particularly limited. For example, (1) a binder component and, if necessary, an optional additive component are added to the color material dispersion according to the present invention, and known mixing is performed. (2) The coloring material, the dispersant, the binder component, and optional addition components as necessary are simultaneously added into the solvent, and a known mixing means is used. (3) A method in which the binder component and, if necessary, an optional additive component are added and mixed in the solvent, and then the colorant dispersion according to the present invention is added thereto and mixed. Etc.

III. Cured product The cured product according to the present invention is a cured product of the colored resin composition according to the present invention.
The cured product according to the present invention can be obtained, for example, by forming a coating film of the colored resin composition according to the present invention, drying the coating film, and then exposing. As a method of forming and exposing a coating film, for example, a method similar to the method used in forming a colored layer provided in the color filter according to the present invention described later can be used.
Moreover, the hardened | cured material which concerns on this invention is used suitably as a colored layer of a color filter.

IV. Color filter The color filter according to the present invention is a color filter including at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product according to the present invention. It is characterized by.

  Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a substrate 1, a light shielding part 2, and a colored layer 3.

<Colored layer>
At least one of the colored layers used in the color filter of the present invention is a cured product according to the present invention, that is, a cured product of the colored resin composition according to the present invention.
The colored layer is usually formed in an opening of a light-shielding part on the substrate to be described later, and is usually composed of a colored pattern of three or more colors.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, solid content concentration, viscosity, and the like of the colored resin composition, but it is usually preferably in the range of 1 to 5 μm.

The colored layer can be formed by the following method, for example.
First, the above-described colored resin composition of the present invention is applied onto a substrate to be described later using an application means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. A wet coating film is formed. Of these, spin coating and die coating can be preferably used.
Next, after drying the wet coating film using a hot plate or an oven, it is exposed through a mask having a predetermined pattern and cured by photopolymerization of an alkali-soluble resin and a polyfunctional monomer. Let it be a coating film. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the colored resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

<Light shielding part>
The light shielding part in the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light shielding part may be a metal thin film such as chromium by sputtering, vacuum deposition or the like. Alternatively, the light shielding part may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring the photosensitive resist, etc. is there.

  The thickness of the light shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and is set to about 0.5 to 2 μm in the case where a black pigment is dispersed or dissolved in a binder resin. Is done.

<Board>
As the substrate, a transparent substrate, a silicon substrate, and a transparent substrate or a substrate in which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed on a transparent substrate or a silicon substrate, which will be described later, are used. On these substrates, another color filter layer, a resin layer, a transistor such as a TFT, a circuit, or the like may be formed.
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, transparent flexible rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible flexible materials such as transparent resin films, optical resin plates, and flexible glasses. Materials.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-1 mm can be used, for example.
The color filter of the present invention may be one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like is formed in addition to the substrate, the light shielding portion, and the colored layer.

V. Display Device A display device according to the present invention includes the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as a liquid crystal display device and an organic light emitting display device.

[Liquid Crystal Display]
Examples of the liquid crystal display device of the present invention include a liquid crystal display device having the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. .
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

  As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After forming the liquid crystal layer by the above-described method, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

[Organic light emitting display]
Examples of the organic light emitting display device of the present invention include an organic light emitting display device having the above-described color filter according to the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view illustrating an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
In addition, Table 1 shows the transmittance at 540 nm when the transmittance at 440 nm of the yellow dye used in each example and each comparative example is 1%. The transmittance is determined by measuring a spectral transmission spectrum in a visible light region of 380 nm or more and 780 nm or less in a dye solution in which a dye is dissolved in methanol so that the transmittance at 440 nm is 1%. Asked. The spectral transmission spectrum was measured using a spectrophotometer UV-2600 manufactured by Shimadzu Corporation.

(Synthesis Example 1: Synthesis of Coumarin Coloring Material A)
A basic (cationic) coumarin dye, 5.0 parts by weight of Basic Yellow 40 (manufactured by Sigma Aldrich) was added to 100 parts by weight of water and 250 parts by weight of methanol (manufactured by Kanto Chemical Co., Ltd.), and dissolved to obtain a coumarin dye solution. Next, the mixture was heated to 65 ° C. with stirring, and 14.0 parts by mass of phosphotungstic acid / n hydrate (manufactured by Nippon Inorganic Chemical Industry, molecular weight 2880 of phosphotungstic acid alone) was dissolved in 100 parts by mass of methanol and added dropwise. Thereafter, the resulting precipitate obtained by reacting for 2 hours was collected by filtration and washed with water. The obtained wet cake was dried to obtain 12.2 parts by mass of a coumarin-based color material A.

(Synthesis Example 2: Synthesis of Coumarin Coloring Material B)
5.0 parts by mass of acidic (anionic) coumarin dye B represented by the following chemical structural formula was added to 300 parts by mass of water and dissolved to obtain a coumarin dye solution. On the other hand, 2.1 parts by mass of polyaluminum chloride (manufactured by Taki Chemical Co., Ltd., trade name Takibine # 1500, molecular weight 174.41) was placed in 200 parts by mass of water and stirred at 80 ° C. to prepare a polyaluminum chloride aqueous solution. The prepared polyaluminum chloride aqueous solution was added dropwise to the dye solution at 80 ° C. over 15 minutes, and the mixture was further stirred for 2 hours. The formed precipitate was collected by filtration and washed with water. The obtained wet cake was dried to obtain 5.2 parts by mass of a coumarin color material B.

(Synthesis Example 3: Synthesis of Cyanine Color Material A)
In Synthesis Example 1, as a cationic dye (basic dye), instead of Basic Yellow 40, Basic Yellow 11 (manufactured by Sigma-Aldrich) was used, and the amount of phosphotungstic acid / n hydrate (manufactured by Nippon Inorganic Chemical Industry) was used. A cyanine-based color material A was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to the amount shown in Table 1.

(Synthesis Examples 4 to 7)
In Synthesis Example 2, the cyanine colors of Synthesis Examples 4 to 7 were the same as those of Synthesis Example 2 except that the amounts of the acid dye, the lake agent and the lake agent used as anions were changed as shown in Table 1. Material B, quinophthalone color material A, quinophthalone color material B, and azo color material A were obtained.
The cyanine dye B used in Synthesis Example 4 is 1-ethyl-3,3-dimethyl-2- (2- (phenylamino) -vinyl) -3H-indole-1- represented by the following chemical structural formula. Ium-5-sulfonate (manufactured by Wako Pure Chemical Industries).

As for the dyes used, Acid Yellow 3 used in Synthesis Examples 5 and 6 is manufactured by Wako Pure Chemical Industries, Ltd., and Acid Yellow 36 used in Synthesis Example 7 is manufactured by Tokyo Chemical Industry Co., Ltd.
Regarding the rake agent used, the polyaluminum chloride used in Synthesis Examples 4, 5, and 7 was (Taki Chemical Co., Ltd., trade name Takibaine # 1500), and the zirconium oxychloride used in Synthesis Example 6 was The product name is Zircosol ZC-20, molecular weight 178.12), manufactured by Elemental Chemical Industries.

(Comparative Synthesis Example 1: Synthesis of quinophthalone color material C)
(1) Synthesis of quinophthalone dye C To 100 parts by mass of methyl benzoate, 60 parts by mass of 6-sulfo-8-aminoquinaldine, 38 parts by mass of phthalic anhydride, and 154 parts by mass of benzoic acid were added and heated to 120 ° C. The mixture was stirred for 4 hours while distilling off water. Next, 50 parts by mass of 2,3-naphthalenedicarboxylic anhydride was further added to the reaction mixture, heated to 180 ° C., and stirred for 4 hours while distilling off water. After cooling to room temperature, the reaction mixture was added to 1200 parts by mass of ethanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with ethanol, and dried under reduced pressure to obtain 114 parts by mass of an acidic (anionic) quinophthalone dye C represented by the following chemical structural formula.

(2) Synthesis of cationic resin 67.3 parts by mass of methyl ethyl ketone was charged into a four-necked separable flask and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts by weight of methyl methacrylate, 28.0 parts by weight of n-butyl methacrylate, 28.0 parts by weight of 2-ethylhexyl methacrylate, 10.0 parts by weight of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4 -Dimethylvaleronitrile) was uniformly made 6.5 parts by mass and 25.1 parts by mass of methyl ethyl ketone, and then charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6830, and then cooled to 50 ° C. To this solution, 3.2 parts by mass of methyl chloride and 22.0 parts by mass of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. In this way, a cationic resin having a cationic group in the side chain of 47% by mass of the resin component was obtained.

(3) Synthesis of quinophthalone-based coloring material C To 2000 parts by mass of water, 51 parts by mass (24 parts by mass of the resin component) of the cationic resin obtained above was added, and after sufficient stirring and mixing, heated to 60 ° C. Thus, a resin solution was prepared. On the other hand, an aqueous solution in which 10 parts by mass of quinophthalone dye C was dissolved in 90 parts by mass of water was prepared and added dropwise to the previously prepared resin solution. After completion of the dropping, the reaction was carried out by stirring at 60 ° C. for 2 hours. The end point of the reaction was judged to be that the quinophthalone-based color material C, which is a salt-forming compound, was obtained, with the reaction solution being dropped onto the filter paper and the point where the bleeding disappeared. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, to obtain 34 parts by mass of a quinophthalone color material C. .

(Comparative Synthesis Example 2: Synthesis of Pigment Yellow 115)
In Synthesis Example 5, pigment was used in the same manner as in Synthesis Example 5 except that barium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of polyaluminum chloride and the amount used was changed to the amount shown in Table 1. Yellow 115 was obtained.

(Synthesis Example 8: Synthesis of block copolymer A and preparation of block copolymer A solution)
A 500 ml 4-neck separable flask was decompressed and dried, and then replaced with Ar (argon). While flowing Ar, 100 g of dehydrated THF, 2.0 g of methyltrimethylsilyldimethylketene acetal, 0.15 ml of 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2 g of mesitylene were added. Thereto, 36.7 g of methyl methacrylate (MMA) was dropped over 45 minutes using a dropping funnel. As the reaction progressed, heat was generated, so the temperature was kept below 40 ° C. by cooling with ice. After 1 hour, 13.3 g of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain block copolymer A. The weight average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 7,600, and the amine value was 95 mgKOH / g.
In a 225 mL mayonnaise bottle, 79.8 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 35.92 parts by mass of block copolymer A (acid value 0 mgKOH / g, amine value 95 mgKOH / g) were added and stirred. A polymer A solution (solid content: 45.0% by mass) was obtained.

(Synthesis Example 9: Preparation of salt type block copolymer A solution)
In 65.2 parts by mass of the block copolymer A solution (solid content: 45.0% by mass) obtained in Synthesis Example 8, 600.8 parts by mass of PGMEA and phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) 1.51 parts by mass were added and stirred at room temperature for 30 minutes to obtain a salt-type block copolymer A solution.

(Synthesis Example 10: Synthesis of alkali-soluble resin A)
A polymerization tank was charged with 150 parts by mass of PGMEA and heated to 100 ° C. in a nitrogen atmosphere, and then 21 parts by mass of methacrylic acid (MAA), 15 parts by mass of methyl methacrylate (MMA), and 50 parts by mass of cyclohexyl methacrylate (CHMA). And 6 parts by mass of perbutyl O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining 100 ° C., and after 2 hours from the completion of dropping of the main chain forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.
Next, while blowing air, 14 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound, and the temperature was raised to 110 ° C. Then, 0.8 parts by mass of triethylamine was added and the mixture was heated at 110 ° C. for 15 hours. By addition reaction, alkali-soluble resin A (weight average molecular weight (Mw) 9020, acid value 90 mgKOH / g, solid content 40% by mass) was obtained.
In addition, the said weight average molecular weight measured the weight average molecular weight by Showex GPC system-21H (Shodex GPC System-21H) by using polystyrene as a standard substance and THF as an eluent. The acid value was measured based on JIS K 0070: 1992.

(Production Example 1: Preparation of photosensitive binder A)
Dipentaerythritol penta (meth) acrylate (Aronix M403 (manufactured by Toagosei Co., Ltd.)) 18 as a polyfunctional monomer with respect to 15.7 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass) obtained in Synthesis Example 10 0.8 parts by mass, Irgacure 907 (photoinitiator having tertiary amine structure: manufactured by BASF) 4.2 parts by mass, NCI-930 (oxime ester photoinitiator: manufactured by ADEKA) 0.7 parts by mass, 60.6 mass parts of PGMEA was added and the photosensitive binder A was obtained.

Example 1
(1) Preparation of Colorant Dispersion Y1 To 3.1 parts by mass of the block copolymer A solution (solid content: 45.0% by mass) obtained in Synthesis Example 8 as a dispersant, propylene glycol monomethyl ether acetate (PGMEA) 24.9 parts by mass, 3.50 parts by mass of the alkali-soluble resin A (solid content 40% by mass) obtained in Synthesis Example 10, and after stirring at room temperature, the coumarin-based colorant A obtained in Synthesis Example 1 3. 50 parts by weight, 35 parts by weight of zirconia beads having a particle size of 2.0 mm were added, shaken for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a preliminary crush, and then 70 parts by weight of zirconia beads having a particle diameter of 0.1 mm And disperse with a paint shaker for 6 hours as the main crushing to obtain a colorant dispersion Y1.

(2) Preparation of colored resin composition Y1 24.6 parts by mass of the colorant dispersion Y1 obtained in (1) above, 34.1 parts by mass of the photosensitive binder A obtained in Production Example 1, and a surfactant mega Facque R08MH (manufactured by DIC) 0.16 parts by mass and 41.1 parts by mass of PGMEA were mixed to obtain a colored resin composition Y1 of Example 1.

(3) Formation of colored layer Using a spin coater, the colored resin composition Y1 obtained in (2) above is formed on a 0.7 mm-thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.). Applied. After drying for 3 minutes on a hot plate at 80 ° C., ultraviolet rays of 60 mJ / cm ² were irradiated using an ultra-high pressure mercury lamp. Thereafter, the film was post-baked in a clean oven at 230 ° C. for 30 minutes to adjust the film thickness to 2.0 μm.

(Examples 2-7, Comparative Examples 1-6)
(1) Preparation of Color Material Dispersions Y2 to Y7 and Comparative Color Material Dispersions YC1 to YC6 The color material dispersion of Example 1 except that the color material shown in Table 2 was used instead of the coumarin-based color material A. In the same manner as Y1, color material dispersions Y2 to Y7 and comparative color material dispersions YC1 to YC6 were obtained.

(2) Preparation of colored resin compositions Y2 to Y7 and comparative colored resin compositions YC1 to YC6 The colored resin of Example 1 except that the colorant dispersion shown in Table 2 was used instead of the colorant dispersion Y1. In the same manner as the composition Y1, colored resin compositions Y2 to Y7 and comparative colored resin compositions YC1 to YC6 were obtained.

(3) Formation of colored layers Y2 to Y7 and colored layers YC1 to YC6 In (3) of Example 1, instead of colored resin composition Y1, colored resin compositions Y2 to Y7 shown in Table 2 and comparative colored resin compositions Colored layers Y2 to Y7 and comparative colored layers YC1 to YC6 were obtained in the same manner as (3) of Example 1 except that the products YC1 to YC6 were used.

[Evaluation]
<Measurement of transmittance>
The colorant dispersions Y1 to Y7 and the comparative colorant dispersions Y1C to YC6 obtained in Examples 1 to 7 and Comparative Examples 1 to 6 are each propylene glycol in such a concentration that the transmittance at 440 nm is 1%. It diluted with monomethyl ether acetate (PGMEA), the spectral transmission spectrum of the visible light region 380 nm or more and 780 nm or less in the coloring material dispersion after the dilution was measured, and the transmittance | permeability in 540 nm was calculated | required from the said spectral transmission spectrum. The spectral transmission spectrum was measured using a spectrophotometer UV-2600 manufactured by Shimadzu Corporation. Table 2 shows the transmittance at 540 nm.

<Heat resistance evaluation>
When forming a colored layer in Examples 1 to 7 and Comparative Examples 1 to 6, L, a, b (L ₀ , a ₀ , b ₀ ) of the colored layer after exposure, and of the colored layer after post-baking Chromaticity (x, y), luminance (Y), L, a, b (L ₁ , a ₁ , b ₁ ) were measured. The chromaticity and luminance were measured using “Microspectrophotometer OSP-SP200” manufactured by Olympus Corporation. A C light source was used as the light source.
As heat resistance evaluation, the color difference (ΔEab) before and after post-baking was calculated from the following formula and evaluated according to the following evaluation criteria.
ΔEab = {(L ₁ −L ₀ ) ² + (a ₁ −a ₀ ) ² + (b ₁ −b ₀ ) ² } ^1/2
(Evaluation criteria)
A: ΔEab is 3 or less B: ΔEab is more than 3 and 5 or less C: ΔEab is more than 5 and less than 10 D: ΔEab is more than 10 And A is even better. If it is C, a slight change in hue is recognized, but it is at a level where there is no problem in practical use of the color filter. If it is D, a clear hue change can be confirmed, which is a problematic level as a color filter.
In Comparative Examples 11 and 12, the luminance (Y) could not be measured.

<Foreign matter evaluation>
The colored layers obtained in Examples 1 to 7 and Comparative Examples 1 to 6 were subjected to surface observation using an optical microscope “MX61L” manufactured by Olympus. The magnification was set to 100, and the number of foreign particles that could be observed by transmission was measured in an area of 500 μm × 500 μm and evaluated according to the following evaluation criteria.
(Evaluation criteria)
AA: Less than 5 (very good)
A: 5 or more and less than 10 (good)
B: 10 or more and less than 20 (a level that causes no problem in use)
C: 20 or more, less than 100 (use problems)
D: 100 or more (use problems)

Here, each abbreviation in the table is as follows.
BY40: Basic Yellow 40 (manufactured by Sigma Aldrich)
AY3: Acid Yellow3 (manufactured by Wako Pure Chemical Industries, Ltd.)
PY138: C.I. I. Pigment Yellow 138 (Daiichi Seika Kogyo Co., Ltd.)
PY150: C.I. I. Pigment Yellow 150 (manufactured by LANXESS)
PY115: C.I. I. Pigment Yellow 115 (Comparative Synthesis Example 2)
Phosphotungstic acid: manufactured by Nippon Inorganic Chemical Industry, phosphotungstic acid / n-hydrate polyaluminum chloride: manufactured by Taki Chemical Co., Ltd., product name TAKIBINE # 1500
Zirconium oxychloride: manufactured by Daiichi Rare Element Chemical Industry, product name: Zircosol ZC-20

(Example 11)
(1) Preparation of Colorant Dispersion G1 As a dispersant, 26.5 parts by mass of the salt-type block copolymer A solution obtained in Synthesis Example 9 was added to the alkali-soluble resin A (solid content 40 obtained in Synthesis Example 10). 3.94 parts by mass) and after stirring at room temperature, 4.55 parts by mass of a green color material (manufactured by DIC, product name FASTGEN GREEN A350) and 35 parts by mass of zirconia beads having a particle size of 2.0 mm are put in reserve. Shake with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour for crushing, then change to 70 parts by mass of zirconia beads with a particle size of 0.1 mm, and disperse for 6 hours with a paint shaker as the main crushing to disperse the colorant A liquid G1 was obtained.

(2) Preparation of colored resin composition G1 The color material dispersion G1 obtained in the above (1) and the color material dispersion Y1 obtained in Example 1 were mixed with a green color material and a coumarin-based color material A. Were mixed at a ratio of 33:67 to obtain a mixed dispersion. 56.3 parts by mass of the obtained mixed dispersion, 19.5 parts by mass of the photosensitive binder A obtained in Production Example 1, 0.4 parts by mass of the surfactant MegaFac R08MH (manufactured by DIC), 23.9 PGMEA Mass parts were mixed to obtain a colored resin composition G1 of Example 11.

(3) Formation of colored layer Using a spin coater, the colored resin composition G1 obtained in (2) above is formed on a 0.7 mm thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.). Applied. After drying for 3 minutes on a hot plate at 80 ° C., ultraviolet rays of 60 mJ / cm ² were irradiated using an ultra-high pressure mercury lamp. Then, the colored layer was formed by post-baking for 30 minutes in a 230 degreeC clean oven. The film thickness of the colored layer was adjusted so that the chromaticity was x = 0.270 and y = 0.680.

(Examples 12-17, Comparative Examples 11-16)
(1) Preparation of colored resin compositions G2 to G7 and comparative colored resin compositions GC1 to GC6 In Example 11 (2), instead of the color material dispersion Y1, the yellow color material dispersion shown in Table 3 was used. In the same manner as in (2) of Example 11 except that the mixed dispersion was obtained so that the mass ratio of the green color material and the yellow color material was as shown in Table 3, the colored resin Compositions G2 to G7 and comparative colored resin compositions GC1 to GC6 were obtained.

(2) Formation of colored layer In Example 11 (3), the above-described colored resin compositions G2 to G7 and comparative colored resin compositions GC1 to GC6 were used instead of the colored resin composition G1, respectively. In the same manner as in Example 11 (3), colored layers G2 to G7 and comparative colored layers GC1 to GC6 were obtained.

  The luminance (Y) and film thickness of the colored layers obtained in Examples 11 to 17 and Comparative Examples 11 to 16 were measured. The luminance was measured using “Microspectrophotometer OSP-SP200” manufactured by Olympus Corporation, and a C light source was used as the light source. The film thickness was measured using “P-17 Stylus Profiler” manufactured by Tencor.

[Summary of results]
From Table 2, the colored layer formed using the colorant dispersion or the colored resin composition of Examples 1 to 7 containing the salt forming colorant of the yellow dye according to the present invention has a small color difference before and after post-baking. The heat resistance was excellent, and the generation of foreign matter was suppressed. On the other hand, in Comparative Examples 1 and 2, foreign matter was generated in the colored layer, and the yellow dye used as the colorant faded during post-baking, so the heat resistance was poor and a usable colored layer could not be formed. . Also in Comparative Example 3, foreign matter was generated in the colored layer and the heat resistance was poor.
Also, from Table 3, the colored layer formed using the colorant dispersion or the colored resin composition of Examples 11 to 17 containing the salt forming colorant of the yellow dye according to the present invention has a decrease in luminance due to heating. Suppressed and high brightness. In addition, the colored layers formed in Examples 11 to 17 were higher in luminance and thinner than Comparative Example 13 using a conventional salt-forming compound using a cationic resin as a chlorinating agent. Further, the colored layers formed in Examples 11 to 17 had higher luminance than Comparative Examples 14 and 15 using a known organic pigment and Comparative Example 16 using a known lake pigment. In particular, in Examples 11 and 12 using a salt-forming color material of a coumarin dye, the luminance was further improved. Further, from the comparison between Example 15 and Example 16, when polyaluminum chloride was used as the counter cation, the colored layer was made thinner than when zirconium oxychloride was used. It has been clarified that the power is improved and the luminance is further improved. In Comparative Examples 11 and 12, since the yellow dye used as the colorant faded during post-baking, the desired chromaticity could not be obtained and a usable colored layer could not be formed.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display device

Claims (8)

Contains a coloring material, a dispersant, and a solvent,
The color material contains a salt forming color material of a yellow dye,
In the salt forming colorant of the yellow dye, when the yellow dye is cationic, the counter ion is a heteropolyacid anion, and when the yellow dye is anionic, the counter ion is a polymetal salt-derived cation. , Colorant dispersion.   2. The color material dispersion according to claim 1, wherein in the salt forming color material of the yellow dye, the yellow dye includes one skeleton selected from the group consisting of an azo skeleton, a quinoline skeleton, a quinophthalone skeleton, a coumarin skeleton, and a cyanine skeleton. liquid. It is a salt coloring material of yellow dye,
When the yellow dye is cationic, the counter ion is a heteropolyacid anion, and when the yellow dye is anionic, the counter ion is a cation derived from a polymetal salt.   The color material according to claim 3, wherein the yellow dye includes one kind of skeleton selected from the group consisting of an azo skeleton, a quinoline skeleton, a quinophthalone skeleton, a coumarin skeleton, and a cyanine skeleton.   A colored resin composition comprising the colorant dispersion according to claim 1 or 2 and a binder component.   A cured product of the colored resin composition according to claim 5.   A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the cured product according to claim 6.   A display device comprising the color filter according to claim 7.

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