JP6256126B2 - Color material dispersion composition, color filter, liquid crystal display device, and organic light emitting display device - Google Patents

Description

  The present invention relates to a color material dispersion composition, a color filter, a liquid crystal display device, and an organic light emitting display device.

Many thin image display devices represented by displays and the like, so-called flat panel displays, have been put on the market, characterized by being thinner than a cathode ray tube type display and taking up little space in the depth direction. The market price has become affordable year by year with the evolution of production technology, the demand has further expanded, and the production volume has been increasing year by year. In particular, color LCD TVs have almost reached the mainstream of TV. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, the amount of light is controlled by electrically driving the liquid crystal, and color expression is performed by the light passing through a color filter. Therefore, a color filter must be present in the color representation of a liquid crystal television and plays a major role in determining the performance of the display. In the organic light emitting display device, when a color filter is used for the white light emitting organic light emitting element, a color image is formed as in the liquid crystal display device.

As a recent trend, there is a demand for power saving of an image display device, and in order to improve the utilization efficiency of a backlight, a high brightness of a color filter is particularly demanded. This is a big problem especially for mobile displays (cell phones, smartphones, tablet PCs).
Although the battery capacity has increased due to technological evolution, the amount of power stored in the mobile is still limited, while the power consumption tends to increase as the screen size increases. An image display device including a color filter affects the design and performance of a mobile terminal in order to be directly linked to the usable time and charging frequency of the mobile terminal.

Here, the color filter is generally formed on a transparent substrate, a transparent layer formed on the transparent substrate, and composed of a colored layer of three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. And a light shielding portion formed.
In such a colored layer forming method, a pigment dispersion method using a pigment having excellent heat resistance and light resistance as a coloring material has been widely used. However, with color filters using pigments, it has become difficult to achieve the current demand for higher brightness.

  As one means for achieving high brightness, a colored resin composition for a color filter using a dye has been studied. Dyes generally have higher transmittance than pigments and can produce high-intensity color filters, but heat resistance and light resistance are poor, and chromaticity is likely to change during high-temperature heating in the color filter manufacturing process. There was a problem. Moreover, the colored resin composition using a dye has a problem that foreign matters are likely to precipitate during the drying process. When foreign matters were deposited on the coating film, the contrast was remarkably deteriorated and it was difficult to use as a colored layer.

As a technique for improving various resistances of dyes, a technique for salting dyes is known.
For example, Patent Document 1 discloses xanthene acid dyes and quaternary grades as blue color compositions for color filters that are excellent in color characteristics, heat resistance, light resistance and solvent resistance and do not generate foreign matter on the coating film. A blue coloring composition for a color filter comprising a salt-forming compound comprising an ammonium salt compound, a colorant containing a blue pigment and a resin is disclosed.

  Patent Document 2 discloses a colorant containing an acidic colorant having a phosphonium cation as a coloring composition suitable for forming a colored layer having high coloring power and high heat resistance and excellent chromaticity characteristics; A coloring composition containing a binder resin and a crosslinking agent is disclosed. The colored composition of Patent Document 2 usually contains a pigment as a colorant, and heat resistance is poor only with the acidic colorant.

  In Patent Document 3, the inventors disclosed a color filter or the like using a specific colorant containing a divalent or higher cation in which a plurality of dye skeletons are cross-linked by a crosslinkable group and a divalent or higher anion. Yes. The above color material contains a divalent or higher cation and a divalent or higher anion to form a molecular aggregate, and is excellent in heat resistance. A color filter using the color material has high contrast, solvent resistance and electrical resistance. It is disclosed that it is excellent in reliability.

Japanese Patent No. 4492760 JP2013-19077A International Publication No. 2012/144521 Pamphlet

The present inventors have studied to use the color material described in Patent Document 3 because it has excellent heat resistance and high brightness can be expected. However, in order to adjust to a desired color tone, it is necessary to use other color materials in combination.
When dioxazine pigments and phthalocyanine pigments that have been conventionally used as other colorants are used, there is a problem that the luminance decreases because the transmittance of the pigments is low. On the other hand, when a dye is used, there is a problem that heat resistance and light resistance are deteriorated, resulting in a decrease in luminance.

  The present invention has been made in view of the above circumstances, and is a color material dispersion composition that is excellent in heat resistance and capable of forming a high-brightness coating film, a high-brightness color filter, a liquid crystal display device having the color filter, and An object is to provide an organic light emitting display device.

  The color material dispersion composition according to the present invention contains (A) a color material, (B) a dispersant, and (C) a solvent, and the (A) color material is represented by the following general formula (I). The coloring material (A-1) and the onium salt (A-2) of a rhodamine acid dye are included.

(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. aliphatic hydrocarbon radical having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, O in the carbon chain, S, may be contained N is .B ^c-'s c-valent poly R ^{i to} R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and ^{R v} represents a bond to be .Ar ¹ to form a ring structure 2 may have a substituent divalent aromatic group. ^R i to R ^v and Ar ¹ there are a plurality of Each may be the same or different.
a is 2, c is an integer of 2 or more, b and d are integers of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

  The color filter according to the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers includes (A) a color material, and (B). And (A) the color material contains a color material (A-1) represented by the above general formula (I) and an onium salt (A-2) of a rhodamine acid dye. It is characterized by.

  In the color material dispersion composition of the present invention and the color filter of the present invention, the onium salt (A-2) of the rhodamine acid dye is selected from the group consisting of ammonium ions, phosphonium ions, iminium ions, and sulfonium ions. The inclusion of one or more selected cations is preferred from the viewpoint of excellent heat resistance and high brightness.

  In the color material dispersion composition of the present invention and the color filter of the present invention, the onium salt (A-2) of the rhodamine acid dye contains an anion represented by the following general formula (II). It is preferable in that it has excellent properties and can achieve high luminance.

(In General Formula (II), R ¹ , R ² , R ³ , and R ⁴ may each independently have a hydrogen atom or a substituent, and include O, S, and N in the carbon chain. R ¹ and R ² , R ³ and R ⁴ may be bonded to each other to form a ring structure, and R ⁵ , R ⁶ and R ⁷ are each independently A halogen atom or a hydrocarbon group which may have a substituent and may contain O, S, N in the carbon chain, and when there are a plurality of R ⁵ , R ⁶ or R ⁷ , R ⁵ , R ⁶ or R ⁷ may be the same or different, p is an integer of 0 to 5, q and r are integers of 0 to 3.
s is sulfonato group having as the substituent for the hydrocarbon group in R ¹ to R ^7, and represents the total number in one molecule of the sulfonato group having as a substituent of xanthene skeleton and a phenyl group, 2-5 integer It is. )

The present invention provides a liquid crystal display device comprising the color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
In addition, the present invention provides an organic light emitting display device comprising the color filter according to the present invention and an organic light emitter.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in heat resistance and can provide the color material dispersion composition which can form a high-intensity coating film, a high-intensity color filter, the liquid crystal display device and organic light-emitting display apparatus which have the said color filter. it can.

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

Hereinafter, the color material dispersion composition, the color filter, the liquid crystal display device, and the organic light emitting display device according to the present invention will be described 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.
In the present invention, the organic group means a group having one or more carbon atoms.

1. Color Material Dispersion Composition The color material dispersion composition according to the present invention contains (A) a color material, (B) a dispersant, and (C) a solvent. It contains a colorant (A-1) represented by (I) and an onium salt (A-2) of a rhodamine-based acidic dye.

(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. aliphatic hydrocarbon radical having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, O in the carbon chain, S, may be contained N is .B ^c-'s c-valent poly R ^{i to} R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and ^{R v} represents a bond to be .Ar ¹ to form a ring structure 2 may have a substituent divalent aromatic group. ^R i to R ^v and Ar ¹ there are a plurality of Each may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

The color material-dispersed composition according to the present invention uses the specific color material (A-1) and the color material (A-2) in combination as the color material (A), and the color material (A) is (C) ) By being dispersed in a solvent, it becomes a color material dispersion composition which is excellent in heat resistance and capable of forming a high-brightness coating film while adjusting to a desired color tone.
In the present invention, the onium salt (A-2) of the rhodamine-based acid dye may hereinafter be simply referred to as a color material (A-2).

Although it is unclear as an effect | action which exhibits the above effects by said specific combination, it is estimated as follows.
The color material (A-1) has a structure represented by the general formula (I), and is a color material in which a divalent or higher cation and a divalent or higher polyacid anion form a salt. The cation in the general formula (I) has a plurality of color development sites, and the color development sites have the same basic skeleton as that of the basic dye. It has a higher molecular weight and better heat resistance than dyes. The present inventors have further improved the heat resistance of the colorant represented by the general formula (I) by combining a divalent or higher cation and a divalent or higher anion to form a molecular aggregate. This is disclosed in Patent Document 3.

On the other hand, the rhodamine-based acid dye is a derivative of 6-aminoxanthene-3-imine, and at least two of the hydrogen atoms in the molecule have at least one of an acidic group such as a sulfo group or a carboxy group and a salt thereof. It is a dye having a structure substituted by a substituent and exhibiting anionic property.
Such a rhodamine-based acidic dye is presumed to be stabilized and excellent in heat resistance because an imine having a cationic property and an acidic group having an anionic property have an inner salt (betaine) structure. In addition, the rhodamine-based acidic dye has an acidic group exhibiting anionic property in addition to the above-described intramolecular salt structure in one molecule, so that the rhodamine-based acidic dye is converted into an onium salt in the solvent. When dispersed as fine particles, a strong electrical interaction or acid-base interaction occurs both inside and between the molecules of the rhodamine dye, and is presumed to have excellent heat resistance.
The rhodamine-based acid dye is a skeleton having an amino group as a substituent, and a coloring portion of the colorant represented by the general formula (I), that is, a triarylmethane skeleton or a xanthene skeleton having an amino group as a substituent. Since it is a similar skeleton, the spectral characteristics have a high transmittance at a wavelength of 400 to 450 nm as in the colorant represented by the general formula (I). Therefore, a color filter without impairing the high transmittance of the color material (A-1) by using a combination of the onium salt (A-2) of the rhodamine acid dye and the color material (A-1). There is also an advantage that it is easy to achieve high brightness.
From the above, by using the color material (A-1) and the color material (A-2) in combination, it is possible to form a coating film with excellent heat resistance and high brightness while adjusting to a desired color tone. A color material dispersion composition can be obtained.

  The color material-dispersed composition of the present invention contains at least (A) a color material, (B) a dispersant, and (C) a solvent, and further within the range not impairing the effects of the present invention. These components may be contained. Hereinafter, each component of the color material dispersion composition of the present invention will be described in order.

(A) Colorant The colorant (A) used in the colorant dispersion composition of the present invention is at least a colorant (A-1) represented by the following general formula (I) and an onium of a rhodamine acid dye. Salt (A-2).

(The symbols in general formula (I) are as described above.)

<Coloring material (A-1)>
A in the general formula (I) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) has no π bond, and the organic group is saturated at least at the terminal directly bonded to N. An aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group is represented, and O (oxygen atom), S (sulfur atom), and N (nitrogen atom) are present in the carbon chain. It may be included. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as the color tone and transmittance of the cationic coloring portion are not affected by the linking group A and other coloring portions, Similar colors can be retained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic unless the terminal carbon atom directly bonded to N has a π bond. The carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain contains O, S, and N. Also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
The aromatic group having an aliphatic hydrocarbon group in A is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N.
Especially, it is preferable that A contains a cyclic | annular aliphatic hydrocarbon group or an aromatic group from the point of the robustness of frame | skeleton.
Among the cyclic aliphatic hydrocarbon groups, a bridged alicyclic hydrocarbon group is preferable from the viewpoint of skeleton fastness. The bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridged structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane. Among the bridged alicyclic hydrocarbon groups, norbornane is preferable. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Among these, the group containing a benzene ring is preferable.
A is preferably divalent from the viewpoint of easy availability of raw materials. For example, when A is a divalent organic group, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic group substituted with 2 alkylene groups having 1 to 20 carbon atoms such as a xylylene group Etc.

The alkyl group in R ^{i to} R ^v is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms can be mentioned, among which a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a straight chain having 1 to 5 carbon atoms. A chain or branched alkyl group is more preferred from the viewpoint of ease of production and raw material procurement. Among them, it is particularly preferred alkyl groups in R ⁱ to R ^v is an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group, and examples of the substituted alkyl group include a benzyl group.
The aryl group in R ^{i to} R ^v is not particularly limited. For example, a phenyl group, a naphthyl group, etc. are mentioned. Examples of the substituent that the aryl group may have include an alkyl group and a halogen atom.

R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v are combined to form a ring structure. R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v form a ring structure through a nitrogen atom Say. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

Among them, from the viewpoint of chemical stability, R ^{i to} R ^v are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v. It is preferable that they are bonded to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

R ^{i to} R ^v can each independently have the above structure. Among them, R ⁱ is preferably a hydrogen atom from the viewpoint of color purity, and R ⁱⁱ to R ^v from the viewpoint of ease of production and raw material procurement. More preferably, R ^v are all the same.

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group may be a heterocyclic group in addition to an aromatic hydrocarbon group composed of a carbocyclic ring. As an aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to a benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; biphenyl, terphenyl, Examples thereof include chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane, and stilbene. The chain polycyclic hydrocarbon may have O, S, and N in the chain skeleton such as diphenyl ether. On the other hand, the heterocyclic ring in the heterocyclic group includes 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; And condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like. These aromatic groups may have a substituent.

  Examples of the substituent that the aromatic group may have include an alkyl group having 1 to 5 carbon atoms and a halogen atom.

Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group composed of a condensed polycyclic carbocycle having 10 to 14 carbon atoms. Among these, a phenylene group or a naphthylene group is more preferable because the structure is simple and the raw material is inexpensive.

A plurality of R ^{i to} R ^v and Ar ¹ in one molecule may be the same or different. In the case where a plurality of R ^{i to} R ^v and Ar ¹ are the same, the color development site exhibits the same color development, so that the same color as the single color development site can be reproduced, which is preferable from the viewpoint of color purity. On the other hand, when at least one of R ^{i to} R ^v and Ar ¹ is a different substituent, a color obtained by mixing a plurality of types of monomers can be reproduced and adjusted to a desired color. it can.

The anion (B ^c− ) of the colorant (A-1) is a diacid or higher polyacid anion. The polyacid anion may be an isopolyacid ion (M _m O _n ) ^d- or a heteropoly acid ion (X _l M _m O _n ) ^d- . 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. Moreover, a counter cation such as Na ⁺ or H ⁺ may be partially included.
Among these, from the viewpoint of high brightness and excellent heat resistance and light resistance, it is preferably a polyacid anion containing at least one of tungsten (W) and molybdenum (Mo), including at least tungsten and containing molybdenum. It is more preferable that it is a good polyacid anion from the viewpoint of heat resistance.

Examples of the polyacid anion containing at least one of tungsten (W) and molybdenum (Mo) include, for example, tungstate ion [W ₁₀ O ₃₂ ] ⁴⁻ and molybdate ion [Mo ₆ O ₁₉ ] ² which are isopolyacids. ^- or a heteropoly acid, ion phosphotungstic acid ^{_{[PW 12 O 40] 3-,}} [P 2 W 18 O 62] 6-, silicotungstic acid ion _{[SiW 12 O} ^{40] 4-,} phosphomolybdic 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 of 1 to 11), [P _{2 W 18-y Mo y O} 62] 6- (y is 1 to 17 integer), Keita ring strike molybdate [SiW ^{_{2-x Mo x O 40]}} 4- (x is 1 to 11 integer), and the like. The polyacid anion containing at least one of tungsten (W) and molybdenum (Mo) is preferably a heteropolyacid among the above from the viewpoint of heat resistance and the availability of raw materials, and more preferably P ( More preferred is a heteropolyacid containing phosphorus.

In the polyacid anion containing at least tungsten (W), the content ratio of tungsten and molybdenum is not particularly limited, but the molar ratio of tungsten to molybdenum is 100: 0 to 85:15 because it is particularly excellent in heat resistance. It is preferable that it is 100: 0 to 90:10.
As the polyacid anion (B ^c− ), the above-mentioned polyacid anions can be used alone or in combination of two or more, and when used in combination of two or more, tungsten and molybdenum in the entire polyacid anion The molar ratio is preferably within the above range.

(Other ions)
The color material (A-1) represented by the general formula (I) may be a double salt containing other cations and anions as long as the effects of the present invention are not impaired. Specific examples of such cations include other basic dyes, organic compounds containing functional groups capable of forming salts with anions such as amino groups, pyridine groups, and imidazole groups, sodium ions, potassium ions, and magnesium ions. Metal ions such as calcium ion, copper ion and iron ion. Specific examples of anions include halide ions such as fluoride ions, chloride ions and bromide ions, and anions of inorganic acids. Examples of the anion of the inorganic acid include anions of oxo acids such as phosphate ions, sulfate ions, chromate ions, tungstate ions (WO ₄ ²⁻ ), and molybdate ions (MoO ₄ ²⁻ ).

<Coloring material (A-2)>
The color material dispersion composition of the present invention contains an onium salt (A-2) of a rhodamine acid dye as a color material.
In the present invention, the rhodamine acid dye is a derivative of 6-aminoxanthene-3-imine, in which at least two of the hydrogen atoms in the molecule are at least one of an acidic group such as a sulfo group and a carboxy group and a salt thereof. It is a dye having a structure substituted by a substituent having an anionic property. Therefore, in the onium salt (A-2) of the rhodamine acid dye, the onium salt is composed of an anion of the rhodamine acid dye and an onium ion described later.
Since the rhodamine-based acidic dye contains an imine moiety exhibiting a cationic property and is anionic as a whole molecule, the substituent having at least one of the acidic group and a salt thereof is usually contained in one molecule. Two or more are included and have at least a pair of intramolecular salts (betaine structure).
In the present invention, such an onium salt of a rhodamine acid dye is used as a color material, and therefore the color material is dispersed in a fine particle state in an organic solvent or a coating film. The dye in the fine particles is aggregated at the molecular level while forming a salt with the onium ion. In the present invention, the betaine structure in the rhodamine-based acid dye molecule enhances electrical interaction, acid-base interaction, and the like both within and between rhodamine-based dye molecules. ) Improves the heat resistance.
In the present invention, the rhodamine-based acidic dye is a derivative of 6-aminoxanthene-3-imine, in particular from the viewpoint of heat resistance, in which at least two of the hydrogen atoms in the molecule have a sulfo group or a salt thereof. It preferably has a structure substituted by

  As the rhodamine-based acid dye, it is preferable to have a phenyl group at the 9-position of the xanthene skeleton, and a structure represented by the following general formula (II) is preferably used.

(In General Formula (II), R ¹ , R ² , R ³ , and R ⁴ may each independently have a hydrogen atom or a substituent, and include O, S, and N in the carbon chain. R ¹ and R ² , R ³ and R ⁴ may be bonded to each other to form a ring structure, and R ⁵ , R ⁶ and R ⁷ are each independently A halogen atom or a hydrocarbon group which may have a substituent and may contain O, S, N in the carbon chain, and when there are a plurality of R ⁵ , R ⁶ or R ⁷ , R ⁵ , R ⁶ or R ⁷ may be the same or different, p is an integer of 0 to 5, q and r are integers of 0 to 3.
s is sulfonato group having as the substituent for the hydrocarbon group in R ¹ to R ^7, and represents the total number in one molecule of the sulfonato group having as a substituent of xanthene skeleton and a phenyl group, 2-5 integer It is. )

Examples of the hydrocarbon group for R ^{1 to} R ⁷ include an alkyl group, an aryl group, and a heteroaryl group.
The alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and is a linear or branched alkyl group having 1 to 8 carbon atoms. Is more preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is more preferable. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, an acidic group or a salt thereof, and the aryl group further includes a halogen atom or an acidic group as a substituent. You may have group or its salt.
Among them, the aryl group in R ^{1 to} R ⁷ is preferably an aryl group which may have a substituent having 6 to 20 carbon atoms, and more preferably a group having a phenyl group, a naphthyl group, or the like.
Furthermore, heteroaryl groups in R ¹ to R ⁷ is, inter alia, preferably heteroaryl group which may have a substituent group having 5 to 20 carbon atoms.
Examples of the substituent that the aryl group or heteroaryl group may have include, for example, an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group or a salt thereof, a hydroxyl group, an alkoxy group, a nitrile group, a carbamoyl group, and a carboxylic acid. An ester group etc. are mentioned.

R ¹ and R ² , R ³ and R ⁴ are bonded to each other to form a ring structure. R ¹ and R ² , R ³ and R ⁴ each form a ring structure through a nitrogen atom. It means being. The ring structure is not particularly limited, and examples thereof include a 5- to 7-membered nitrogen-containing heterocyclic ring, and specific examples include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

In the general formula (II), s represents the total number in one molecule of the sulfonate group having R ^{1 to} R ⁷ as a substituent of the hydrocarbon group and the sulfonate group having a xanthene skeleton and a phenyl group as a substituent. Represents an integer of 2 to 5. From the viewpoint of heat resistance, s is preferably 3 to 5.
In addition, it shows the structure of the rhodamine-based acid dye at the time of forming the general formula (II) onium salt, and the rhodamine-based acid dye as a raw material is a sulfo group (—SO ₃ ^— ) ₃ H), a sulfonate group (—SO ₃ M, where M represents a metal atom). Examples of the metal atom M include a sodium atom and a potassium atom.

  Specific examples of rhodamine acid dyes include Acid Red 50, Acid Red 52, Acid Red 289, Acid Violet 9, Acid Violet 30, Acid Blue 19 and the like.

In the present invention, the rhodamine acid dye forms an onium salt with an onium ion.
In the present invention, the onium ion refers to an ion produced by coordination of a cation-type atomic group such as a proton or an alkyl cation with a compound containing an atom having a lone pair of electrons, and the onium salt refers to the onium ion. A compound containing
Examples of onium ions include ammonium ion [N (R) ₄ ] ⁺ , phosphonium ion [P (R) ₄ ] ⁺ , iminium ion [(R) ₂ —N═C (R) ₂ ] ⁺ , arsonium Ion [As (R) ₄ ] ⁺ , stibonium ion [Sb (R) ₄ ] ⁺ , oxonium ion [O (R) ₃ ] ⁺ , sulfonium ion [S (R) ₃ ] ⁺ , selenonium ion [Se (R) ₃ ] ⁺ , stannonium ion [Sn (R) ₃ ] ⁺ , iodonium ion [I (R) ₂ ] ⁺ , diazonium ion [R—N ⁺ ≡N] and the like. In the present invention, the onium ion is preferably at least one selected from the group consisting of an ammonium ion, an iodonium ion, a sulfonium ion, a diazonium ion, and a phosphonium ion from the viewpoint of heat resistance. And at least one selected from the group consisting of phosphonium ions, iminium ions and sulfonium ions.
In addition, R in the ionic formula of the onium ion is a hydrocarbon group which may independently have a hydrogen atom or a substituent and may have a hetero atom in the carbon chain.
Examples of the hetero atom that may be contained in the carbon chain include a nitrogen atom, a phosphorus atom, an arsenic atom, an antimony atom, an oxygen atom, a sulfur atom, a selenium atom, a tin atom, and an iodine atom. In the present invention, the onium ions may be divalent or higher onium ions by having these atoms.

The hydrocarbon group in R in the ionic formula of the onium ion is not particularly limited. Specific examples of the hydrocarbon group include an alkyl group, an aryl group, a heteroaryl group, and the like. Further, any R in the molecule may be bonded to form a ring structure. Specific examples of the hydrocarbon group and the substituent that may be included include the same hydrocarbon groups as those in R ^{1 to} R ⁷ .
As an example in which Rs in a molecule are bonded to each other to form a ring structure, for example, imidazolium, pyridinium, etc. having an iminium ion in a heterocycle are preferable.

Specific examples of the onium ion include tetramethylammonium cation, tetraethylammonium cation, monostearyltrimethylammonium cation, distearyldimethylammonium cation, diallyldimethylammonium cation, tristearylmonomethylammonium cation, cetyltrimethylammonium cation, and trioctylmethylammonium cation. Cation, dioctyldimethylammonium cation, monolauryltrimethylammonium cation, dilauryldimethylammonium cation, trilaurylmethylammonium cation, triamylbenzylammonium cation, trihexylbenzylammonium cation, trioctylbenzylammonium cation, trilaurylbenzylan Cation, trimethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dibutylethylsulfonium cation, Examples include dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, and trimethyldecylphosphonium cation. But it is not limited to these. In this invention, onium ion can be used individually by 1 type or in combination of 2 or more types.
In the present invention, as the onium ion, an onium salt compound in which the desired onium ion and an arbitrary counter anion form a salt can be used as a raw material. Specific examples of the counter anion include halide ions such as chloride ion, bromide ion and iodide ion, hexafluorophosphate ion, and the like.

The onium salt of a rhodamine acid dye can be obtained by mixing a desired rhodamine acid dye and an onium salt compound containing a desired onium ion in a solvent. Specifically, for example, (1) a desired rhodamine-based acidic dye and a desired onium salt compound are added to a solvent in which the dye and the onium salt compound are soluble, and heating or cooling is performed as necessary. (2) A step of separately preparing a desired rhodamine-based acidic dye solution and a desired onium salt compound solution, the dye solution, and the onium salt compound solution are required. And a method for producing an onium salt of a rhodamine-based acidic dye having a step of mixing while heating or cooling. In the present invention, the method (2) is preferred from the viewpoint of high yield.
When using the method of (2), it is preferable to drop and mix the said onium salt compound solution in the said rhodamine type | system | group acidic dye solution over 5 to 30 minutes. Although the temperature at the time of reaction of a rhodamine type | system | group acidic dye solution and onium salt compound solution is not specifically limited, It is preferable to set it as 5-90 degreeC.
The rhodamine-based acid dye may be synthesized with reference to a known method such as a synthesis method described in Yutaka Hosoda “New Dye Chemistry” Gihodo etc., or a commercially available product may be used.

<Other colorants>
(A) A color material may mix | blend another color material as needed for the purpose of control of a color tone in the range which does not impair the effect of this invention. As the other colorant, for example, a conventionally known pigment or dye can be selected according to the purpose, and one or more kinds can be used.
As the other coloring material, use the coloring material described in International Publication No. 2012/144521 pamphlet including a divalent or higher cation in the general formula (I) and an arbitrary divalent or higher anion. Is preferred.
Specific examples of other color materials include C.I. I. Pigment violet 1, C.I. I. Pigment violet 2, C.I. I. Pigment violet 3, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23; C.I. I. Pigment blue 1, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment red 81, C.I. I. And pigments such as CI Pigment Red 82 and dyes such as Acid Red.

When using other color materials, the blending amount is not particularly limited. Among them, the color material described in the pamphlet of International Publication No. 2012/144521 including a divalent or higher cation represented by the general formula (I) and an arbitrary divalent or higher anion is used as another colorant. When used, it can be suitably used at an arbitrary ratio.
The blending amount of the other color material is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, with respect to (A) 100 parts by mass of the total color material. Within this range, the color tone can be controlled without impairing the high transmittance characteristics, heat resistance, and light resistance characteristics of the color material represented by the general formula (I). .

The average dispersed particle size of the color material (A) used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a colored layer of a color filter. From the viewpoint of excellent heat resistance and light resistance, it is preferably in the range of 10 to 200 nm, and more preferably in the range of 20 to 150 nm. (A) Since the average dispersed particle diameter of the color material is in the above range, a liquid crystal display device and an organic light emitting display device manufactured using the color material dispersed composition of the present invention have high contrast and high quality. It can be.
The average dispersed particle diameter of the (A) color material in the color material dispersion composition is the dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, and measured by a laser light scattering particle size distribution meter. It is to be measured. As the measurement of the particle size with a laser light scattering particle size distribution meter, the color material dispersion composition is appropriately diluted to a concentration that can be measured with a laser light scattering particle size distribution meter with a solvent used in the color material dispersion composition (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 analyzer (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.

In the color material dispersion composition of the present invention, the content of the color material is not particularly limited. The content of the color material is preferably in the range of 5 to 40% by mass, and more preferably 10 to 20% by mass with respect to the total amount of the color material dispersion composition, from the viewpoint of dispersibility and dispersion stability.
Moreover, in the color material dispersion composition of the present invention, the mixing ratio of the color material (A-1) and the color material (A-2) may be appropriately set in order to prepare a desired color tone, and is not particularly limited. . From the viewpoint of heat resistance, the mass ratio of the coloring material (A-1) to the coloring material (A-2) is preferably 50:50 to 99: 1, and preferably 70:30 to 95: 5. More preferred.

(B) Dispersant In the color material dispersion composition of the present invention, (A) the color material is dispersed in a solvent with (B) a dispersant and used. (B) The dispersant can be appropriately selected from those conventionally used as dispersants. As specific examples of the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine 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 (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 and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes Long chain polyaminoamide phosphates; polyethylenimine derivatives (amides and their bases obtained by reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters); polyallylamine derivatives (polyallylamine and free carboxyls) Polyester, polyamide or ester-amide co-condensation with groups The reaction product obtained by reacting one or more compound selected from among the three compounds of (polyester amide)), and the like.

  Examples of such commercially available dispersants include Disperbyk-2000, 2001, BYK-LPN6919, 21116 (above, manufactured by Big Chemie Japan), Azisper PB821, 881 (manufactured by Ajinomoto Co., Inc.), and the like. be able to. Among these, BYK-LPN6919 and 21116 are preferable from the viewpoint of heat resistance, electrical reliability, and dispersibility.

As the polymer dispersant, among them, a polymer having at least a structural unit represented by the following general formula (IV) from the viewpoint that the colorant (A) can be suitably dispersed and the dispersion stability is good, And it is preferable that it is 1 or more types selected from the group which consists of a urethane type dispersing agent which consists of a compound which has a 1 or more urethane bond (-NH-COO-) in 1 molecule.
Hereinafter, the preferable dispersant will be described in detail.

<Polymer having at least a structural unit represented by the following general formula (IV)>
In the present invention, as the dispersant (B), a polymer having at least a structural unit represented by the following general formula (IV) can be suitably used.

(In the general formula (IV), R ¹¹ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, Q is a group represented by the following general formula (IV-a), or a substituted group. Represents a nitrogen-containing heterocyclic group which may have a group and can form a salt.)

(In General Formula (IV-a), R ¹² and R ¹³ each independently represent a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R ¹² and R ¹³ may be the same or different from each other. May be.)

In general formula (IV), A is a direct bond or a bivalent coupling group. The direct bond means that Q is directly bonded to the carbon atom in the general formula (IV) without a linking group.
Examples of the divalent linking group in A include 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” are each independently an alkylene group), combinations thereof, and the like.
Among these, from the viewpoint of dispersibility, A in the general formula (IV) is preferably a direct bond, a -CONH- group, or a divalent linking group containing a -COO- group.

  Moreover, it can use especially suitably by salt-forming the structural unit represented by the said general formula (IV) of these dispersing agents by the following salt forming agent in arbitrary ratios.

Examples of the polymer having the structural unit represented by the general formula (IV) include WO2011 / 108495 pamphlet, JP2013-054200A, JP2010-237608A, and JP2011-75661A. The block copolymer and graft copolymer having the structure described in 1. can improve the dispersibility and dispersion stability of the coloring material and the heat resistance of the resin composition, and can form a colored layer with high brightness and high contrast. To preferred.
Moreover, BYK-LPN6919 etc. are mentioned as a commercial item of the polymer which has a structural unit represented by general formula (IV).

(Salt forming agent)
A preferred dispersant of the present invention is a polymer in which at least a part of the nitrogen moiety of the structural unit represented by the general formula (IV) forms a salt (hereinafter sometimes referred to as salt modification).
In the present invention, a salt forming agent is used to form a salt at the nitrogen site of the structural unit represented by the general formula (IV). By doing so, the dispersibility and dispersion stability of the color material are improved. As the salt forming agent, acidic organic phosphorus compounds, organic sulfonic acid compounds, quaternizing agents and the like described in WO2011 / 108495 pamphlet and JP2013-054200A can be suitably used. In particular, when the salt-forming agent is an acidic organic phosphorus compound, the surface of the coloring material is phosphate because the salt-forming site containing the acidic organic phosphorus compound of the dispersant is localized on the particle surface of the coloring material. Since it is in a coated state, attack (hydrogen abstraction) of the coloring material by the active oxygen to the dye skeleton is suppressed, and the heat resistance and light resistance of the coloring material including the dye skeleton are improved. For this reason, when a polymer salt-modified with an acidic organic phosphorus compound is used as a dispersant, fading during high-temperature heating can be further suppressed in a state in which the colorant (A) with high transmittance used in the present invention is well dispersed. Thus, a colored layer with higher luminance can be formed even through a high-temperature heating process in the color filter manufacturing process.

<Urethane-based dispersant>
The urethane-based dispersant suitably used as the dispersant is a dispersant composed of a compound having one or more urethane bonds (—NH—COO—) in one molecule.
By using a urethane-based dispersant, good dispersion can be achieved with a small amount. By making the amount of the dispersant small, it is possible to relatively increase the amount of the curing component and the like, and as a result, it is possible to form a colored layer having excellent heat resistance.

  As the urethane dispersant in the present invention, among others, (1) polyisocyanates having two or more isocyanate groups in one molecule, (2) polyesters having a hydroxyl group at one end or both ends, and one end or It is preferably a reaction product with one or more selected from poly (meth) acrylates having hydroxyl groups at both ends, and (1) polyisocyanates having two or more isocyanate groups in one molecule; (2) at least one selected from polyesters having a hydroxyl group at one or both ends, and poly (meth) acrylates having a hydroxyl group at one or both ends, and (3) active hydrogen in the same molecule And a reaction product of a compound having a basic group or an acidic group.

  Examples of commercially available urethane dispersants include Disperbyk-161, 162, 163, 164, 167, 168, 170, 171, 174, 182, 183, 184, 185, BYK-9077 (above, Big Chemie Japan Co., Ltd.) Product), Ajisper PB711 (manufactured by Ajinomoto Co., Inc.), EFKA-46, 47, 48 (manufactured by EFKA CHEMICALS) and the like. Among these, Disperbyk-161, 162, 166, 170, and 174 are preferable from the viewpoint of heat resistance, electrical reliability, and dispersibility.

(C) Solvent In the present invention, the (C) solvent does not react with each component in the colorant dispersion composition, and can be appropriately selected from solvents that can dissolve or disperse them. Specifically, organic solvents such as alcohols, ether alcohols, esters, ketones, ether alcohol acetates, ethers, aprotic amides, lactones, unsaturated hydrocarbons, saturated hydrocarbons are used. Among them, it is preferable to use an ester solvent from the viewpoint of solubility during dispersion and coating suitability.

Preferred ester solvents include, for example, methyl methoxypropionate, ethyl ethoxypropionate, methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl Acetate, ethoxyethyl acetate, ethyl cellosolve acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,6-hexanediol diacetate, diethylene glycol monoethyl ether acetate, Examples include diethylene glycol monobutyl ether acetate.
Among them, it is preferable to use propylene glycol monomethyl ether acetate (PGMEA) from the viewpoint of low risk to the human body and low volatility near room temperature but good heat drying properties. In this case, there is a merit that a special cleaning step is not required even when switching to a colored resin composition using conventional PGMEA.
These solvents may be used alone or in combination of two or more.

(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 composition of this invention as needed.
Examples of the dispersion auxiliary resin include alkali-soluble resins 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 coloring material dispersion composition of the present invention includes both a colored resin composition containing a binder component described later and a pre-preparation of the colored resin composition not containing a binder component. Hereinafter, when it is necessary to particularly distinguish the color material dispersion composition in the present invention, an embodiment containing the binder component may be referred to as a colored resin composition, and an embodiment not containing the binder component is referred to as a color material dispersion. There is.

When the color material dispersion composition of the present invention is used as a coating film for color filter applications, it is preferable to further contain a binder component in order to impart film formability and adhesion to the surface to be coated. Especially, in order to provide sufficient hardness to a 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 the colorant dispersion composition can be selectively deposited in a pattern on a substrate to form a colored layer, for example, when used in an inkjet method, the curable binder component does not need developability. In this case, a well-known thermosetting binder component, a photosensitive binder component, etc. which are used when forming a color filter colored layer by an inkjet system etc. can be used suitably.
As the thermosetting binder, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst capable of promoting a thermosetting reaction may be added. Examples of the thermosetting functional group include an epoxy group, an oxetanyl group, an isocyanate group, and an ethylenically unsaturated bond. An epoxy group is preferably used as the thermosetting functional group. Specific examples of the thermosetting binder component include those described in International Publication No. 2012/144521 pamphlet.

On the other hand, when using a photolithography process when forming a colored layer, the photosensitive binder component which has alkali developability is used suitably.
Hereinafter, although the photosensitive binder component is demonstrated, a curable binder component is not limited to these. In addition to the photosensitive binder component described below, a thermosetting binder component that can be polymerized and cured by heating such as an epoxy resin may be further used.

  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 color material dispersion composition of the present invention, a negative photosensitive binder component is preferable because a pattern can be easily formed by an existing process by a photolithography method.
Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator constituting the negative photosensitive binder component will be specifically described.

(1) Alkali-soluble resin The alkali-soluble resin in the present invention has an acidic group, acts as a binder resin, and is preferably used in a developer used for pattern formation, particularly preferably soluble in an alkali developer. It can be appropriately selected and used.
The preferred alkali-soluble resin in the present invention is preferably a resin having a carboxyl group as an acidic group. Specifically, an acrylic copolymer having a carboxyl group, an epoxy (meth) acrylate resin having a carboxyl group, etc. Can be mentioned. Among these, particularly preferred are those having a carboxyl 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. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the colorant dispersion composition.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the colorant dispersion composition, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

Specific examples of the acrylic copolymer having a carboxyl group include those described in International Publication No. 2012/144521 pamphlet. Specifically, for example, methyl (meth) acrylate, ethyl ( Examples thereof include a copolymer composed of a monomer having no carboxyl group, such as (meth) acrylate, and one or more selected from (meth) acrylic acid and its anhydride. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, a polymer having an ethylenically unsaturated bond introduced, for example, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly suitable in that the colored layer becomes more stable.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the resulting coating film in an alkaline developer is lowered, and pattern formation becomes difficult. On the other hand, when the copolymerization ratio exceeds 50% by mass, there is a tendency that the formed pattern is easily detached from the substrate or the pattern surface is roughened during development with an alkali developer.

  The preferred molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 500,000, pattern formation may be difficult during development with an alkaline developer.

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material 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. Specific examples include those described in International Publication No. 2012/144521 pamphlet. Each of the epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride may be used alone or in combination of two or more.

  The alkali-soluble resin used in the color material-dispersed composition may be used singly or in combination of two or more, and the content thereof is the color material 100 contained in the colored resin composition. It is usually in the range of 10 to 1000 parts by mass, preferably in the range of 20 to 500 parts by mass with respect to parts by mass. If the content of the alkali-soluble resin is too small, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is too large, the ratio of the coloring material is relatively low, which is sufficient. The coloring density may not be obtained.

(2) Multifunctional monomer The polyfunctional monomer used in the colorant dispersion composition is not particularly limited as long as it can be polymerized by a photoinitiator described later, and usually has 2 ethylenically unsaturated double bonds. A compound having two or more is used, and a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferable.
Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples include those described in International Publication No. 2012/144521 pamphlet.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. When the color material dispersion composition of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three (trifunctional) or more polymerizable double bonds. Some are preferable, and poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Succinic acid modification of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate Acid-modified product, dipentaerythritol hexa Meth) acrylate are preferable.
The content of the polyfunctional monomer used in the color material dispersion composition is not particularly limited, but is usually about 5 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. It is a range. If the content of the polyfunctional monomer is less than the above range, the photocuring may not sufficiently proceed and the exposed part may be eluted, and if the content of the polyfunctional monomer is more than the above range, the alkali developability may be deteriorated. There is.

(3) Photoinitiator There is no restriction | limiting in particular as a photoinitiator used in a color material dispersion | distribution composition, It uses combining 1 type (s) or 2 or more types from the conventionally well-known various photoinitiators. it can. Specific examples include those described in International Publication No. 2012/144521 pamphlet.

  Content of the photoinitiator used in a color material dispersion composition is about 0.01-100 mass parts normally with respect to 100 mass parts of said polyfunctional monomers, Preferably it is 5-60 mass parts. If this content is less than the above range, the polymerization reaction cannot be sufficiently caused, so that the hardness of the colored layer may not be sufficient. On the other hand, if the content is more than the above range, the colorant dispersion composition In some cases, the content of the coloring material or the like in the solid content is relatively low, and a sufficient coloring density may not be obtained.

  In the color material dispersion composition of the present invention, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, an adhesion promoter, etc. Etc. may be contained.

<Combination ratio of each component in the colorant dispersion composition>
(1) When the color material dispersion composition is a colored resin composition containing a binder component (A) The total content of the color material is 3 to 65% by mass with respect to the total solid content of the color material dispersion composition, More preferably, it is blended at a ratio of 4 to 55% by mass. If it is more than the said lower limit, the coloring layer at the time of apply | coating a color material dispersion 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 the dispersibility and dispersion stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. In the present invention, the solid content is everything except the above-mentioned solvent, and includes a liquid polyfunctional monomer.
In addition, the content of the (B) dispersant is not particularly limited as long as (A) the color material can be uniformly dispersed. For example, the total solid content of the color material dispersion composition 3 to 40% by mass can be used. Furthermore, it is preferable to mix | blend in the ratio of 5-35 mass% with respect to the solid content whole quantity of a color material dispersion composition, and it is preferable to mix | blend especially in the ratio of 5-25 mass%. If it is more than the said lower limit, (A) It is excellent in the dispersibility and dispersion stability of a coloring material, and is excellent in storage stability. Moreover, if it is below the said upper limit, developability will become favorable.
The total amount of these binder components is preferably 10 to 92% by mass, preferably 15 to 87% by mass, based on the total solid content of the colorant dispersion composition. If it is more than the said lower limit, the colored layer which has sufficient hardness and 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.
Moreover, what is necessary is just to set suitably content of (C) solvent in the range which can form a colored layer accurately. Usually, it is preferably in the range of 55 to 95% by mass, more preferably in the range of 65 to 88% by mass, based on the total amount of the colorant dispersion composition containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

(2) When the color material dispersion composition is a color material dispersion containing no binder component When the color material dispersion composition is a color material dispersion containing no binder component, (A) the content of the color material is dispersed. From the viewpoints of colorability and dispersion stability, it is preferably in the range of 5 to 40% by mass, more preferably 10 to 20% by mass, based on the total amount of the colorant dispersion.
When the color material dispersion composition is a color material dispersion containing no binder component, the content of the (B) dispersant is usually 1 to 50% by mass, and more preferably 1 to 20% by mass with respect to the total amount of the dispersion. It is preferable from the viewpoint of dispersibility and dispersion stability.
Moreover, when a color material dispersion composition is a color material dispersion liquid which does not contain a binder component, (C) solvent is 45-94 mass% normally with respect to the whole quantity of a color material dispersion liquid, Preferably it is 60-85. It is prepared using a ratio by mass. When there is too little solvent, a viscosity will rise and a dispersibility will fall easily. Moreover, when there are too many solvents, color material density | concentration will fall, and when adding a binder component and preparing a colored resin composition, it may be difficult to achieve a target chromaticity coordinate.
In addition, the color material dispersion liquid which does not contain a binder component is used as a preliminary preparation for preparing the colored resin composition. That is, in the present invention, the color material dispersion is preliminarily prepared in the previous stage of preparing the colored resin composition, (color material component mass in the composition) / (solid content other than the color material component in the composition). It is a colorant dispersion having a high (mass) ratio. Specifically, the ratio of (mass of color material component in composition) / (mass of solid content other than color material component in composition) is usually 1.0 or more. By mixing the colorant dispersion and at least the binder component, a colored resin composition having excellent dispersibility can be prepared.

<Method for Producing Color Material Dispersion Composition>
The method for producing a color material dispersion composition comprises (A) a color material, (B) a dispersant, (C) a solvent, and various additive components such as a binder component used as desired. The material is not particularly limited as long as the material can be uniformly dispersed in (C) the solvent from (B) the dispersant, and can be prepared by mixing using a known mixing means.
As a method for preparing the color material dispersion composition, for example, (1) (A) a color material, (B) a dispersant, and (C) a solvent are mixed to prepare a color material dispersion, (2) (C) Solvent, (A) Colorant, (B) Dispersing agent, binder component, etc. (3) In (C) solvent, (B) dispersant and various additive components used as desired such as a binder component are added and mixed. Thereafter, (A) a method of adding and mixing a coloring material;
Among these methods, the method (1) is preferable because it can effectively prevent aggregation of the color material and can be uniformly dispersed. In the method (1), the color material dispersion may be prepared by any method as long as (A) the color material can be uniformly dispersed in a solvent by a dispersant, and known mixing means can be used. .
As a method for preparing the colorant dispersion, (B) the dispersant is mixed and stirred in the solvent (C) to prepare a dispersant solution, and then the (A) colorant and, if necessary, the dispersant solution. A dispersion can be prepared by mixing other components and dispersing using a known stirrer or disperser. Alternatively, the color material dispersion liquid in which the color material (A-1) is dispersed and the color material dispersion liquid in which the color material (A-2) is dispersed may be separately prepared and mixed.

  Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibrating ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. 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 0.10 to 1.0 mm.

  Specifically, preliminary dispersion is performed with 2 mm zirconia beads having a relatively large bead diameter, and main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a membrane filter of 0.5 to 5.0 μm after dispersion.

2. Color filter The color filter according to the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers comprises (A) a colorant, ( B) a dispersant, wherein the color material (A) is a color material (A-1) represented by the following general formula (I) and an onium salt (A-2) of a rhodamine-based acid dye. It is characterized by including.

(The symbols in general formula (I) are as described above.)

  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 transparent 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 includes a coloring material (A-1) represented by the general formula (I) and an onium salt (A-2) of a rhodamine acid dye. Is a layer.
The colored layer is usually formed in an opening of a light shielding part on a transparent substrate, which will be described later, and is usually composed of three or more colored patterns.
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, the solid content concentration, the viscosity, and the like of the color material dispersion composition, but is usually preferably in the range of 1 to 5 μm.

The colored layer containing the color material (A-1) represented by the general formula (I) used in the color filter of the present invention and the onium salt (A-2) of a rhodamine-based acid dye is the above-described (A A coloring material, (B) a dispersing agent, (C) a solvent, and a binder component, wherein the (A) coloring material is represented by the general formula (I); It is preferably formed using a color material dispersion composition containing an onium salt (A-2) of a rhodamine-based acidic dye, and is preferably a cured product of the color material dispersion composition. For example, when the colorant dispersion composition is a photosensitive resin composition, the colored layer can be formed by the following method.
First, the color material dispersion composition is applied onto a transparent substrate, which will be described later, using a coating means such as a spray coating method, a dip coating method, a bar coating method, a coal coating method, or a spin coating method to form a wet coating film. Let me.
Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized. A photosensitive coating film is used. 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 color material dispersion 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 colorant dispersion 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.

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a transparent substrate 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. Examples of the light-shielding portion include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. The metal thin film may be a CrO _x film (x is an arbitrary number) and a laminate of two Cr films, and a CrO _x film (x is an arbitrary number) with a reduced reflectance. , CrN _y film (y is an arbitrary number) and three layers of Cr film may be laminated.
When the light shielding part is a material in which a black color material is dispersed or dissolved in a binder resin, the light shielding part can be formed by any method that can pattern the light shielding part, and is not particularly limited. For example, a photolithography method, a printing method, an ink jet method and the like using the colored resin composition for the light shielding part can be exemplified.

  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 about 0.5 to 2 μm in the case where a black color material is dispersed or dissolved in a binder resin. Is set.

(Transparent substrate)
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, a transparent rigid material having no flexibility such as quartz glass, alkali-free glass, or synthetic quartz plate, or a flexible or flexible resin such as a transparent resin film, an optical resin plate, or flexible glass. A transparent flexible material is mentioned.
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 transparent substrate, the light shielding portion, and the colored layer. .

5. Liquid Crystal Display Device A liquid crystal display device according to the present invention includes 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 30 having an electrode substrate 22 on a transparent substrate 23, and the color filter 10 and the counter substrate 30. The liquid crystal layer 25 is formed, and the transparent electrode film 21 is provided between the color filter 10 and the liquid crystal layer 25.
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.
The substrate 21 and the substrate 22 can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention. For example, the substrate 21 and the substrate 22 have a transparent electrode and an alignment film on a transparent substrate. can do.
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.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. In addition, the liquid crystal layer can be formed by overlapping the color filter and the counter substrate under reduced pressure and bonding them with a sealant. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

6). Organic Light-Emitting Display Device An organic light-emitting display device according to the present invention includes the color filter according to the present invention described above and an organic light-emitting body.
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.

(Synthesis Example 1: Synthesis of Color Material α)
(1) Synthesis of Intermediate 1 Referring to the method for producing Intermediate 3 and Intermediate 4 described in International Publication No. 2012/144521, 15.9 g of Intermediate 1 represented by the following chemical formula (1) ( Yield 70%).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), divalent and elemental analysis values: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (78.06%) , 7.75%, 7.69%)

(2) Synthesis of blue color material α The intermediate 1 5.00 g was added to 300 ml of water and dissolved to obtain an intermediate 1 solution. Next, 10.44 g of phosphotungstic acid · n hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O manufactured by Nippon Inorganic Chemical Industry was put in 100 ml of water to prepare an aqueous phosphotungstic acid solution. The aqueous phosphotungstic acid solution prepared above was mixed with the intermediate 1 solution, and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g (yield 98%) of a blue color material α corresponding to the color material (A-1) represented by the following chemical formula (2).
The obtained compound was confirmed to be the target compound from the following analysis results. (Molar ratio W / Mo = 100/0)
MS (ESI) (m / z): 510 (+), divalent, elemental analysis value: CHN measured value (41.55%, 5.34%, 4.32%); theoretical value (41.66%) (5.17%, 4.11%)

(Synthesis Example 2: Synthesis of Color Material β)
Acid Red 289 (manufactured by Tokyo Chemical Industry Co., Ltd., 5.0 g of rhodamine acid dye (the following chemical formula (3)) was added to 500 ml of water and dissolved at 80 ° C. to prepare a dye solution. Dimethyl distearyl ammonium chloride (effective solid content 95.5%) was dissolved in 85 g of isopropyl alcohol to prepare a dimethyl distearyl ammonium chloride solution, which was cooled to 5 ° C. in an ice bath and prepared. The dimethyldistearyl ammonium chloride solution was added dropwise to the dye solution over 25 minutes at 5 ° C., and the mixture was further stirred for 1 hour at 5 ° C. The resulting precipitate was collected by filtration and washed with water. Is dried to give 9.07 g of a colorant β corresponding to the onium salt (A-2) of the rhodamine acid dye (yield 97 ) Was obtained.

(Synthesis Example 3: Synthesis of Color Material γ)
5.0 g of Acid Red 289 was added to 500 ml of water and dissolved at 80 ° C. to prepare a dye solution. 3.17 g of ethoxycarbonylmethyl (triphenyl) phosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in 200 ml of water and stirred at 80 ° C. to prepare an ethoxycarbonylmethyl (triphenyl) phosphonium bromide aqueous solution. The prepared aqueous solution of ethoxycarbonylmethyl (triphenyl) phosphonium bromide was added dropwise to the dye solution at 80 ° C. over 15 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The formed precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 4.46 g (yield 60%) of a coloring material γ corresponding to the rhodamine-based acidic dye onium salt (A-2).

(Synthesis Example 4: Synthesis of Color Material δ)
5.0 g of Acid Red 289 was added to 500 ml of water and dissolved at 40 ° C. to prepare a dye solution. Separately, 3.49 g of benzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 30 ml of about 5 wt% hydrochloric acid aqueous solution and stirred to obtain benzimidazole hydrochloride, then dissolved in 170 ml of water and stirred at 40 ° C. A hydrochloride aqueous solution was prepared. The prepared benzimidazole hydrochloride aqueous solution was added dropwise to the dye solution at 40 ° C. over 20 minutes, and the mixture was further stirred at 40 ° C. for 1 hour. The formed precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 3.97 g (yield 48%) of a colorant δ corresponding to the rhodamine-based acidic dye onium salt (A-2).

(Synthesis Example 4: Synthesis of Binder Resin A)
A reactor equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer was charged with 130 parts by mass of diethylene glycol ethyl methyl ether (abbreviated as EMDG) as a solvent, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. After that, a mixture containing 32 parts by mass of methyl methacrylate, 22 parts by mass of cyclohexyl methacrylate, 24 parts by mass of methacrylic acid, 2.0 parts by mass of AIBN as an initiator and 4.5 parts by mass of n-dodecyl mercaptan as a chain transfer agent. It was dripped continuously over 1.5 hours.
Thereafter, the reaction was continued while maintaining the synthesis temperature, and 0.05 parts by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of the dropping.
Next, while blowing air, 22 parts by mass of glycidyl methacrylate was added, the temperature was raised to 110 ° C., 0.2 parts by mass of triethylamine was added, and an addition reaction was carried out at 110 ° C. for 15 hours. 44 mass% solid content) was obtained.
The obtained binder resin A had a mass average molecular weight (Mw) of 8500, a number average molecular weight (Mn) of 4200, a molecular weight distribution (Mw / Mn) of 2.02, and an acid value of 85 mgKOH / g.

(Preparation Example 1: Preparation of salt type block polymer dispersant A solution)
In the reactor, 60.74 parts by mass of PGMEA, a block copolymer containing a tertiary amino group (trade name: BYK-LPN6919, manufactured by Big Chemie) (amine value 120 mgKOH / g, solid content 60% by weight) 35.64 parts by mass (21.38 parts by mass of effective solid content) were dissolved, 3.62 parts by mass of PPA (0.5 molar equivalent to the tertiary amino group of the block copolymer) was added, and the mixture was stirred at 40 ° C. for 30 minutes. Thus, a salt type block polymer dispersant A solution (solid content: 25%) was prepared.

(Preparation Example 2: Preparation of binder composition A)
19.82 parts by mass of PGMEA, 18.18 parts by mass of binder resin A (solid content: 44% by mass) of Synthesis Example 4, 5-6 functional acrylate monomer (trade name: Aronix M403, manufactured by Toagosei Co., Ltd.), 8.00 parts by mass, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF) 3.00 parts by mass, 2,4 diethylthioxanthone (trade name: Binder composition A (solid content 40% by mass) was prepared by mixing 1.00 parts by mass of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.).

(Example 1: Preparation of colorant dispersion composition A)
(1) 12.15 parts by mass of the colorant α of Synthesis Example 1, 0.85 parts by mass of the colorant β of Synthesis Example 2, and 20.80 parts by mass of the salt-type block polymer dispersant A solution prepared in Preparation Example 1 (Effective solid content 5.20 parts by mass), Binder resin A 11.82 parts by mass (effective solid content 5.20 parts by mass) of Synthesis Example 4 and 54.38 parts by mass of PGMEA are mixed, and paint shaker (manufactured by Asada Tekko) Was dispersed for 1 hour with 2 mm zirconia beads as a pre-dispersion, and further for 6 hours with 0.1 mm zirconia beads as a main dispersion, and a colorant dispersion A was obtained.
(2) 28.57 parts by mass of the colorant dispersion A obtained in (1) above, 28.29 parts by mass of the binder composition A obtained in Preparation Example 2, 43.14 parts by mass of PGMEA, and surfactant R08MH 0.04 parts by mass (manufactured by DIC) and 0.4 parts by mass of silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) were added and mixed, followed by pressure filtration to obtain a colorant dispersion composition A.

(Example 2: Preparation of colorant dispersion composition B)
A color material dispersion B was prepared in the same manner as in (1) of Example 1 except that the color material γ was used instead of the color material β in Example 1 (1).
Next, in Example 1 (2), the color material dispersion composition B was prepared in the same manner as in Example 1 (2) except that the color material dispersion B was used instead of the color material dispersion A. Obtained.

(Example 3: Preparation of colorant dispersion composition C)
A color material dispersion C was prepared in the same manner as in (1) of Example 1 except that color material δ was used instead of color material β in Example 1 (1).
Next, in (2) of Example 1, the color material dispersion composition C was prepared in the same manner as in (2) of Example 1 except that the color material dispersion C was used instead of the color material dispersion A. Obtained.

(Comparative Examples 1-4: Preparation of Comparative Colorant Dispersion Composition)
(1) Comparative color material dispersions D to G were prepared in the same manner as in (1) of Example 1 except that the color material was changed to that shown in Table 1 below in (1) of Example 1. .
(2) Preparation of Comparative Color Material Dispersion Compositions D to G In Example 1 (2), Comparative Color Material Dispersions D to G were used in place of Color Material Dispersion A, respectively. Comparative colorant dispersion compositions D to G were obtained in the same manner as (2).
In Table 1, “Coloring material ε” represents Pigment Blue 15: 6, and “Coloring material ζ” represents Pigment Bio Red 23.

(Evaluation)
<Optical performance evaluation, heat resistance evaluation>
The color material dispersion composition obtained in each example and comparative example was applied onto a 0.7 mm thick glass substrate (manufactured by Nippon Electric Glass Co., Ltd., “OA-10G”) using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (blue colored layer) was obtained by irradiating ultraviolet rays of 40 mJ / cm ² using an ultrahigh pressure mercury lamp. The film thickness after drying and curing is set to target chromaticity y = 0.082, and the chromaticity (x, y) and luminance (Y) of the obtained colored substrate are set to “Microspectrophotometer OSP-SP200” manufactured by Olympus. ”And measured. The substrate on which the colored film was formed was post-baked for 30 minutes in a 230 ° C. clean oven, and the chromaticity (x, y) and luminance (Y) of the obtained colored film were measured again. If the luminance (Y) before and after the post-bake treatment is 10 or more, the heat resistance is high and the transparency is high, which is excellent as a blue pixel for a color filter.
The results are shown in Table 2.

[Summary of results]
Obtained by using the color material dispersion composition of Examples 1 to 3 in which the color material (A-1) represented by the general formula (I) and the onium salt compound (A-2) of the rhodamine acid dye are combined. The obtained colored layer has a brightness (Y) before and after the post-baking treatment of 10 or more compared with those of conventionally known Comparative Examples 1 to 4, and has high heat resistance and high transparency. It was revealed that a bright color filter can be obtained.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 21 Transparent electrode film 22 Electrode substrate 23 Transparent substrate 25 Liquid crystal layer 30 Opposite substrate 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Positive Hole transport layer 74 Light-emitting layer 75 Electron injection layer 76 Cathode 80 Organic light-emitting body 100 Organic light-emitting display device

Claims (8)

(A) a color material, (B) a dispersant, and (C) a solvent, wherein the color material (A-1) is represented by the following general formula (I): A colorant dispersion composition comprising an onium salt (A-2) of a rhodamine acid dye.
(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. aliphatic hydrocarbon radical having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, O in the carbon chain, S, may be contained N is .B ^c-'s c-valent poly R ^{i to} R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and ^{R v} represents a bond to be .Ar ¹ to form a ring structure 2 may have a substituent divalent aromatic group. ^R i to R ^v and Ar ¹ there are a plurality of Each may be the same or different.
a is 2, c is an integer of 2 or more, b and d are integers of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )   The color according to claim 1, wherein the onium salt (A-2) of the rhodamine-based acidic dye contains one or more cations selected from the group consisting of ammonium ions, phosphonium ions, iminium ions, and sulfonium ions. Material dispersion composition. The color material dispersion composition according to claim 1 or 2, wherein the onium salt (A-2) of the rhodamine acid dye contains an anion represented by the following general formula (II).
(In General Formula (II), R ¹ , R ² , R ³ , and R ⁴ may each independently have a hydrogen atom or a substituent, and include O, S, and N in the carbon chain. R ¹ and R ² , R ³ and R ⁴ may be bonded to each other to form a ring structure, and R ⁵ , R ⁶ and R ⁷ are each independently A halogen atom or a hydrocarbon group which may have a substituent and may contain O, S, N in the carbon chain, and when there are a plurality of R ⁵ , R ⁶ or R ⁷ , R ⁵ , R ⁶ or R ⁷ may be the same or different, p is an integer of 0 to 5, q and r are integers of 0 to 3.
s is sulfonato group having as the substituent for the hydrocarbon group in R ¹ to R ^7, and represents the total number in one molecule of the sulfonato group having as a substituent of xanthene skeleton and a phenyl group, 2-5 integer It is. ) A color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers contains (A) a color material and (B) a dispersant, (A) A color filter in which the color material includes a color material (A-1) represented by the following general formula (I) and an onium salt (A-2) of a rhodamine-based acidic dye.
(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. aliphatic hydrocarbon radical having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, O in the carbon chain, S, may be contained N is .B ^c-'s c-valent poly R ^{i to} R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and ^{R v} represents a bond to be .Ar ¹ to form a ring structure 2 may have a substituent divalent aromatic group. ^R i to R ^v and Ar ¹ there are a plurality of Each may be the same or different.
a is 2, c is an integer of 2 or more, b and d are integers of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )   The color according to claim 4, wherein the onium salt (A-2) of the rhodamine-based acid dye contains one or more cations selected from the group consisting of ammonium ions, phosphonium ions, iminium ions, and sulfonium ions. filter. The color filter according to claim 4 or 5, wherein the onium salt (A-2) of the rhodamine acid dye contains an anion represented by the following general formula (II).
(In General Formula (II), R ¹ , R ² , R ³ , and R ⁴ may each independently have a hydrogen atom or a substituent, and include O, S, and N in the carbon chain. R ¹ and R ² , R ³ and R ⁴ may be bonded to each other to form a ring structure, and R ⁵ , R ⁶ and R ⁷ are each independently A halogen atom or a hydrocarbon group which may have a substituent and may contain O, S, N in the carbon chain, and when there are a plurality of R ⁵ , R ⁶ or R ⁷ , R ⁵ , R ⁶ or R ⁷ may be the same or different, p is an integer of 0 to 5, q and r are integers of 0 to 3.
s is sulfonato group having as the substituent for the hydrocarbon group in R ¹ to R ^7, and represents the total number in one molecule of the sulfonato group having as a substituent of xanthene skeleton and a phenyl group, 2-5 integer It is. )   A liquid crystal display device comprising: the color filter according to claim 4; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.   An organic light emitting display device comprising the color filter according to claim 4 and an organic light emitter.