JPWO2018025498A1 - Colored composition, color filter and method of manufacturing the same, liquid crystal display device, and light emitting display device - Google Patents

Abstract

(A) a color material, (B) a dispersant, (C) a binder component, (D) a fluorine-containing polymer, and (E) a solvent, wherein the (A) color material is a dye Provided is a coloring composition containing a salt coloring material, wherein the (D) fluorine-containing polymer comprises a thermally decomposable fluorine-containing polymer from which a fluorine-containing group is released in a temperature range of 100 ° C. to 250 ° C.

Description

  Embodiments of the present disclosure relate to a coloring composition, a color filter and a method of manufacturing the same, a liquid crystal display device, and a light emitting display device.

  With the development of personal computers, especially portable personal computers, the demand for liquid crystal displays is increasing. The prevalence of LCD TVs for home use is also increasing, and the market for LCDs is expanding. In recent years, a light emitting display such as an organic EL display having high visibility due to self light emission is also attracting attention as a next-generation image display. 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 for these display devices. For example, in the formation of a color image of a liquid crystal display device, light passing through a color filter is colored as it is to the color of each pixel constituting the color filter, and light of those colors is combined to form a color image. In the light emitting display device, when a color filter is used for the light emitting element emitting white light, a color image is formed as in the liquid crystal display device.
Under such circumstances, also in the color filter, there is a growing demand for higher luminance, higher contrast, and improved color rendition.
Here, the color filter is generally formed on a transparent substrate, a colored layer formed on the transparent substrate and made of colored patterns of three primary colors of red, green and blue, and a transparent substrate so as to separate each colored pattern. And a light shielding portion formed.

  As one means for achieving high brightness, a colored resin composition using a dye as a composition for forming a colored layer has been studied. Dyes generally have higher transmittance than pigments and can produce color filters of high brightness. However, there is a problem that the dye is easily discolored by ultraviolet irradiation and the like, and the luminance of the colored layer is easily reduced.

  On the other hand, high smoothness is required for the colored layer of the color filter from the viewpoint of reducing color unevenness and the like. As a means to improve smoothness, it is known to add a leveling agent or the like to the colored resin composition. However, the leveling agent may be unevenly distributed on the surface of the colored layer, which may reduce the wettability of the surface. Therefore, when providing a protective layer etc. on a colored layer, there existed a problem that the composition for the said resin layer was easy to be repelled in the colored layer surface, and a coating-film nonuniformity was easy to arise. As means for solving this problem, there is known a method of improving the wettability of the surface of the colored layer by providing an ultraviolet ray cleaning step of irradiating the surface of the colored layer with ultraviolet light.

  Also, for example, Patent Document 1 provides a composition that can impart high smoothness to each pixel of a color filter and a protective film of the pixel, and can favorably apply a coating agent or the like on the pixel or the protective film. As a possible resin, a fluorine-containing thermally decomposable resin having a specific structure is disclosed.

JP, 2016-17172, A

  An embodiment of the present disclosure provides a colored composition having high brightness, high smoothness, and capable of forming a colored layer that is easy to form a covering layer on the surface, a color filter having a high brightness and smooth colored layer, and An object of the present invention is to provide a manufacturing method thereof, a liquid crystal display device having the color filter, and a light emitting display device.

One embodiment of the present disclosure contains (A) a colorant, (B) a dispersant, (C) a binder component, (D) a fluorine-containing polymer, and (E) a solvent,
The (A) colorant contains a dye-forming salt colorant,
The coloring composition is provided, wherein the (D) fluorine-containing polymer comprises a thermally decomposable fluorine-containing polymer in which a fluorine-containing group is released in a temperature range of 100 ° C. or more and 250 ° C. or less.

One embodiment of the present disclosure contains (A) a colorant, (B) a dispersant, (C) a binder component, (D) a fluorine-containing polymer, and (E) a solvent,
The (A) colorant contains a dye-forming salt colorant,
A coloring composition in which the (D) fluorine-containing polymer is a polymer including at least one structure selected from the following general formula (1-1) and the following general formula (1-2) in a side chain I will provide a.

（一般式（１−１）及び一般式（１−２）中、Ｌ^１は、酸素原子、又は硫黄原子を表し、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子、置換基を有してもよい炭素原子数が１個以上１８個以下の炭化水素基を表し、Ｒ_ｆはフッ素原子を有するアルキル基、又は、フッ素原子を有するポリアルキレンエーテル基を表す。Ｒ^１とＲ_ｆは結合して環構造を形成してもよい。）

(In the general formula (1-1) and the general formula (1-2), L ¹ represents an oxygen atom or a sulfur atom, and R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent R _f represents a fluorine atom-containing alkyl group or a fluorine atom-containing polyalkylene ether group, and R ¹ and R each represent a hydrocarbon group having 1 to 18 carbon atoms which may have one or more carbon atoms. _f may combine to form a ring structure)

  One embodiment of the present disclosure provides a colored composition in which the (A) coloring material comprises one or more selected from a triarylmethane-based coloring material and a xanthene-based coloring material.

  One embodiment of the present disclosure provides a coloring composition in which the (A) coloring material contains a coloring material represented by the following general formula (I).

（一般式（Ｉ）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎが含まれてもよい脂肪族炭化水素基、又は、Ｎと直接結合する末端に脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎが含まれてもよい芳香族基を表し、
Ｒ^ｉ、Ｒ^ｉｉ、Ｒ^ｉｉｉ、Ｒ^ｉｖ、及びＲ^ｖは各々独立に水素原子、置換基を有してもよいアルキル基又は置換基を有してもよいアリール基を表し、Ｒ^ｉｉとＲ^ｉｉｉ、Ｒ^ｉｖとＲ^ｖが結合して環構造を形成してもよい。
Ｒ^ｖｉ、及びＲ^ｖｉｉは各々独立に置換基を有してもよいアルキル基又は置換基を有してもよいアルコキシ基を表し、
Ａｒ^ｉは置換基を有してもよい２価の芳香族基を表し、
Ｂ^ｃ−は、ｃ価のアニオンを表し、
ａ及びｃは２以上の整数を、ｂ及びｄは１以上の整数を、ｅは０又は１を、ｆ及びｇは０以上４以下の整数を表し、ｆ＋ｅ及びｇ＋ｅは０以上４以下であり、
複数あるＲ^ｉ〜Ｒ^ｖｉｉ、Ａｒ^ｉ、ｅ、ｆ及びｇは、同一であっても異なっていてもよい。）

(In general formula (I), A is an a-valent organic group in which a carbon atom directly bonded to N does not have a π bond, and the organic group is a saturated aliphatic carbon group at the end directly linked to N Aliphatic hydrocarbon group which has a hydrogen group and may contain O, S, N in its carbon chain, or has an aliphatic hydrocarbon group at the end directly bonded to N, and has O in its carbon chain , S and N represent an aromatic group which may be contained,
R ^{i, R ii,} R ^{iii, R iv,} and ^{R v} each independently represent a hydrogen atom, which may have a an optionally substituted alkyl group or a substituted aryl ^{group, R ii} and R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure.
R ^vi and R ^vii each independently represent an alkyl group which may have a substituent or an alkoxy group which may have a substituent,
Ar ⁱ represents a divalent aromatic group which may have a substituent,
B ^c- represents a c-valent anion,
a and c are integers of 2 or more, b and d are integers of 1 or more, e is 0 or 1, f and g are integers of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less ,
Plural R ^{i to} R ^vii , Ar ⁱ , e, f and g may be the same or different. )

  One embodiment of the present disclosure is a color filter having a colored layer on a transparent substrate, wherein at least one of the colored layers is a cured product of a colored composition showing an embodiment of the present disclosure. provide.

  One embodiment of the present disclosure provides a color filter further having a covering layer on the colored layer.

One embodiment of the present disclosure is a method of manufacturing a color filter having a colored layer on a transparent substrate,
Forming a coating film of the coloring composition according to one embodiment of the present disclosure on a transparent substrate;
Curing the coating (ii);
And a step (iii) of heating the cured coating film.

One embodiment of the present disclosure further includes the step (iv) of forming a covering layer on the colored layer after the step (iii),
There is provided a method for producing a color filter, which does not have an ultraviolet ray cleaning step between the step (iii) and the step (iv).

  One embodiment of the present disclosure provides a liquid crystal display device including a color filter according to one embodiment of the present disclosure, an opposing substrate, and a liquid crystal layer formed between the color filter and the opposing substrate. Do.

  One embodiment of the present disclosure provides a light emitting display having a color filter according to one embodiment of the present disclosure and an organic light emitter.

  According to an embodiment of the present disclosure, a colored composition having high brightness, high smoothness, and capable of forming a colored layer that can easily form a covering layer on the surface, and a color having a high brightness and smooth colored layer A filter and a method of manufacturing the same, and a liquid crystal display and a light emitting display having the color filter can be provided.

It is a schematic sectional drawing which shows one Embodiment of a color filter. It is a schematic sectional drawing which shows one Embodiment of a color filter. It is a schematic sectional drawing which shows one Embodiment of a liquid crystal display device. FIG. 1 is a schematic cross-sectional view illustrating an embodiment of an organic light emitting display device.

Hereinafter, embodiments of the present disclosure, examples, and the like will be described with reference to the drawings and the like. However, the present disclosure can be implemented in many different modes, and is not interpreted as being limited to the description contents of the embodiments and the examples illustrated below. In addition, the drawings may be schematically represented with respect to the width, thickness, shape, etc. of each portion in comparison with the actual embodiment in order to clarify the description, but this is merely an example, and the interpretation of the present disclosure It is not limited. In the specification and the drawings, the same elements as those described above with reference to the drawings already described may be denoted by the same reference numerals, and the detailed description may be appropriately omitted. Moreover, although it may be demonstrated using the words "upper" or "lower" for convenience of explanation, the vertical direction may be reversed.
In the present specification, when there is a certain configuration such as a certain member or a certain region “above (or below)” another configuration such as another member or another region, unless there is a particular limitation, This includes not only directly above (or just below) other configurations, but also above (or below) other configurations, ie, other configurations between (or below) other configurations. Also includes the case where the element is included.

In the present disclosure, light includes electromagnetic waves of wavelengths in visible and non-visible regions, and also radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present disclosure, (meth) acrylic represents each of acrylic and methacrylic, and (meth) acrylate represents each of acrylate and methacrylate.

1. Colored Composition The colored composition of the present disclosure contains (A) a colorant, (B) a dispersant, (C) a binder component, (D) a fluorine-containing polymer, and (E) a solvent,
The (A) colorant contains a dye-forming salt colorant,
The (D) fluorine-containing polymer includes a thermal decomposition-type fluorine-containing polymer in which a fluorine-containing group is released in a temperature range of 100 ° C. or more and 250 ° C. or less.

  The coloring composition of the present disclosure has high brightness and high smoothness and forms a coating layer on the surface by using a salt-forming coloring material of a dye and a specific thermally-degradable fluorine-containing polymer in combination. An easy colored layer can be formed.

  Conventionally, high smoothness is required for the colored layer of the color filter from the viewpoint of reducing color unevenness and the like. In order to improve the smoothness, it has been practiced to add a fluorine-based leveling agent to the coloring composition. However, the leveling agent may be unevenly distributed on the surface of the colored layer, which may reduce the wettability of the surface. Therefore, in the case where a coating layer such as a protective layer or an alignment film is provided on the colored layer, there is a problem that the composition for forming the coating layer is easily repelled on the surface of the colored layer and coating unevenness easily occurs. As means for solving this problem, a method of improving the wettability of the surface of the colored layer has been carried out by providing an ultraviolet ray cleaning step of irradiating the surface of the colored layer with ultraviolet light. Conventionally, as a coloring material in a coloring composition, a pigment excellent in light resistance is generally used. Therefore, according to the above-mentioned method, a colored layer having good smoothness and a coating layer having no coating unevenness are used. It was possible to form. On the other hand, from the viewpoint of further increasing the brightness of the color filter, the present inventors have studied to form a colored layer using a coloring composition containing a dye. When the said ultraviolet-ray washing | cleaning process was applied to the colored layer containing a dye, it turned out that the brightness of a colored layer may fall on the contrary. As a result of intensive studies based on such findings, the present inventors have high brightness and high smoothness by using a combination of a salt-forming coloring material of a dye and a specific thermally-degradable fluorine-containing polymer. It has been found that it is possible to form a colored layer that is likely to form a coating on the surface.

The coloring composition of this indication contains the salt-forming coloring material of dye as a (A) coloring material. By using a dye, high brightness can be achieved, and heat resistance is also improved by forming a dye.
Moreover, since the coloring composition of this indication contains a specific thermal decomposition-type fluorine-containing polymer as (D) fluorine-containing polymer, the coloring layer formed using the said coloring composition has high smoothness. . Furthermore, when forming a protective layer etc. further on the said colored layer, the fluorine which the (D) fluorine-containing polymer which is unevenly distributed on the colored layer surface by heating the said colored layer at 100 degreeC or more and 250 degrees C or less Since the containing group detaches and the wettability of the surface is improved, it is possible to suppress the coating unevenness of the protective layer and the like. From such a thing, since the ultraviolet-ray washing | cleaning process conventionally performed in order to improve the wettability of the surface becomes unnecessary, the fall of a brightness | luminance is suppressed even if it is a colored layer containing the dye which was easy to fade by ultraviolet light. A colored layer of high brightness is obtained.
Thus, the coloring composition of the present disclosure has high brightness and high smoothness by using a combination of a salt-forming coloring material of a dye and a specific thermally-degradable fluorine-containing polymer, and a coating layer on the surface Can be formed easily.

The coloring composition according to the embodiment of the present disclosure contains at least (A) a colorant, (B) a dispersant, (C) a binder component, (D) a fluorine-containing polymer, and (E) a solvent. And may contain other components as needed.
Hereinafter, with respect to such a coloring composition, (D) the fluorine-containing polymer will be described first, and then each component will be described in order.

(D) Fluorine-Containing Polymer In the embodiment of the present disclosure, the (D) fluorine-containing polymer includes a thermally decomposable fluorine-containing polymer from which a fluorine-containing group is separated in a temperature range of 100 ° C. or more and 250 ° C. or less. The thermally decomposable fluorine-containing polymer has a fluorine-containing group before heating, so that the coating film of the coloring composition can be smoothed, and the fluorine-containing group can be formed by heating after curing of the coating film. It releases and improves the wettability of the surface of a colored layer, and it becomes easy to form a coating layer.

  In the present disclosure, the thermally decomposable fluorine-containing polymer is not particularly limited as long as at least a part of the fluorine-containing group is separated in a temperature range of 100 ° C. or more and 250 ° C. or less. Examples of the fluorine-containing group leaving in a temperature range of 100 ° C. to 250 ° C. include, for example, a fluorine-containing group bonded to a polymer via an acetal bond, a hemiacetal bond, a thioacetal bond, a thiohemiacetal bond, etc. Be Among them, high smoothness is obtained, and after heating, it contains one or more types of structures selected from the following general formula (1-1) and the following general formula (1-2) from the viewpoint of improving the surface wettability. Is preferred.

（一般式（１−１）及び一般式（１−２）中、Ｌ^１は、酸素原子、又は硫黄原子を表し、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子、置換基を有してもよい炭素原子数が１個以上１８個以下の炭化水素基を表し、Ｒ_ｆはフッ素原子を有するアルキル基、又は、フッ素原子を有するポリアルキレンエーテル基を表す。Ｒ^１とＲ_ｆは結合して環構造を形成してもよい。）

(In the general formula (1-1) and the general formula (1-2), L ¹ represents an oxygen atom or a sulfur atom, and R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent R _f represents a fluorine atom-containing alkyl group or a fluorine atom-containing polyalkylene ether group, and R ¹ and R each represent a hydrocarbon group having 1 to 18 carbon atoms which may have one or more carbon atoms. _f may combine to form a ring structure)

When the thermally decomposable fluorine-containing polymer contains one or more types of structures selected from the general formula (1-1) and the general formula (1-2), the fluorine-containing group containing R _f by heating is It is assumed that the polymer-side end is, for example, a hydroxy group or a carboxy group. On the other hand, it is presumed that the released fluorine-containing group has a relatively low boiling point and is unlikely to remain on the surface of the colored layer due to volatilization and the like. As a result, it is presumed that the surface of the colored layer after heating is improved in both hydrophilicity and lipophilicity and wettability is improved.

The hydrocarbon group having 1 to 18 carbon atoms in R ¹ , R ² and R ³ includes an alkyl group having 1 to 18 carbon atoms and 7 to 18 carbon atoms. The following aralkyl groups, aryl groups having 6 to 18 carbon atoms, and the like can be mentioned.
The alkyl group may be linear, branched or cyclic and, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, cyclopentyl group, cyclohexyl group, bornyl group And isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group substituted adamantyl group and the like.
Examples of the aralkyl group include benzyl group, phenethyl group, naphthylmethyl group, biphenyl methyl group and the like, which may further have a substituent. Further, as the aryl group, a phenyl group, biphenyl group, naphthyl group And a tolyl group, a xylyl group, etc., and may further have a substituent.
As a substituent which the alkyl group part of the said alkyl group and the said aralkyl group may have, halogen atoms, such as F, Cl, Br, a hydroxyl group, etc. are mentioned, for example. Moreover, as a substituent of the aromatic ring which the said aryl group and the said aralkyl group have, C1-C4 linear or branched alkyl group, a halogen atom, a hydroxyl group etc. are mentioned.
In addition, carbon number of a substituent is not contained in the said preferable carbon number.
In the embodiment of the present disclosure, R ^{1 to} R ³ are each independently preferably a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, and each independently a hydrogen atom or a methyl group. Or an ethyl group is more preferable, each independently a hydrogen atom or a methyl group is even more preferable, and any ^one of R ^{1 to} R ³ is particularly preferably a hydrogen atom.

The alkyl group having a fluorine atom in R _f may be an alkyl group in which at least one or more hydrogen atoms are substituted by a fluorine atom. The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and is preferably an alkyl group having 10 carbon atoms or less. The alkyl group having a fluorine atom has 1 or more carbon atoms to which a fluorine atom is directly bonded, but from the viewpoint of smoothness, the number of carbon atoms to which a fluorine atom is directly bonded is preferably 4 or more. Furthermore, from the environmental point of view, the alkyl group having a fluorine atom preferably has 6 or less carbon atoms to which the fluorine atom is directly bonded.
The alkyl group may be linear, branched or cyclic, and specifically, it is an alkyl group similar to R ^{1 to} R ³ and at least one hydrogen atom is fluorine What is substituted by the atom is mentioned. In R _f , one in which at least four or more hydrogen atoms are substituted by fluorine atoms is preferable.
In addition, the polyalkylene ether group having a fluorine atom in R _f may be a polyalkylene ether group in which at least one or more hydrogen atoms are substituted with a fluorine atom. As the polyalkylene ether group, _{^{e.g., -R 4 - (OR 4)}} m -OR 4 ', in (m group and the like represented is 0 to 17 an integer, ^{R 4} is a carbon atom An alkylene group having 1 to 6 carbon atoms, R ^{4 ′} is an alkyl group having 1 to 6 carbon atoms, and a plurality of R ^{4 s} may be the same as or different from each other.) .
The alkylene group for the R ^4, a methylene group, an ethylene group, a propylene group and the like, other fluorine atom as a substituent, a chlorine atom, a bromine atom, may have an alkyl group, the substituent The alkyl group as R may further have a fluorine atom as a substituent. Moreover, as an alkyl group in said R ^{4 '} , a methyl group, an ethyl group, a propyl group etc. are mentioned, You may have a chlorine atom and a bromine atom other than a fluorine atom as a substituent.

The fact that R ¹ and R _f combine to form a ring structure means that R ¹ and R ^f form a ring structure via L ¹ and in this case, at least one fluorine atom in the ring structure As long as it has it.

Examples of the preferred R _f structure include, but are not limited to, the following.

（ｍ、ｍ’、ｎ、及びｎ’は、それぞれ独立に、１以上１８以下の整数である）

(M, m ', n and n' are each independently an integer of 1 or more and 18 or less)

In the above formula, n is preferably 2 or more, more preferably 4 or more, and on the other hand, preferably 12 or less, more preferably 8 or less, still more preferably 6 or less.
In the above formula, n ′ is preferably 2 or more, while preferably 6 or less, more preferably 4 or less, still more preferably 3 or less.
In the above formula, m is preferably 2 or more, more preferably 4 or more, and on the other hand, preferably 10 or less, more preferably 8 or less.
In the above formula, m ′ is preferably 2 or more, more preferably 4 or more, and on the other hand, preferably 8 or less, more preferably 6 or less.

  In the embodiment of the present disclosure, the thermally decomposable fluorine-containing polymer preferably has a structural unit represented by the following general formula (2).

（一般式（２）中、Ｒ^５は水素原子又はメチル基、Ｌ^２は直接結合又は２価の連結基、Ｑ^１は、前記一般式（１−１）又は前記一般式（１−２）で表される置換基である。）

(In the general formula (2), R ⁵ is a hydrogen atom or a methyl group, L ² is a direct bond or a divalent linking group, and Q ¹ is a group represented by the general formula (1-1) or the general formula (1-2) A substituent represented by

In the present disclosure, L ² means a direct bond means that Q ¹ is directly bonded to a carbon atom of the main chain skeleton without a linking group. The divalent linking group for L ² is not particularly limited as long as it can be linked to a carbon atom of the main chain skeleton and Q ¹ . Examples of the divalent linking group for L ² include a linear, branched or cyclic alkylene group, (—COO-L ^3- (L ³ is a linear, branched or cyclic alkylene group), etc. Further, the alkylene group may have an oxy group (-O-) in the carbon chain. A methylene group, ethylene group, a propylene group etc. are mentioned as the said alkylene group, You may have a chlorine atom, a bromine atom, an alkyl group etc. other than a fluorine atom as a substituent.
In the embodiments of the present disclosure, L ² is preferably a direct bond or (—COO-L ³ —), among others.

  In the present disclosure, the method for producing the thermally decomposable fluorine-containing polymer is not particularly limited. For example, in the case of producing a thermally decomposable fluorine-containing polymer including one or more types of structures selected from the general formula (1-1) and the general formula (1-2), it is selected from hydroxy group and carboxy group Is a fluorine-containing monomer by introducing a compound represented by the following general formula (3) into a polymerizable monomer having one or more types of substituents, and then the monomer, and, if necessary, other monomers The polymer may be polymerized to form a fluorine-containing polymer having a constituent unit containing a fluorine-containing group, and may further comprise a constituent unit having one or more substituents selected from a hydroxy group and a carboxy group, and further optionally A polymer having another structural unit, and introducing a compound represented by the following general formula (3) into at least one substituent selected from a hydroxy group and a carboxy group in the polymer It is, by a structural unit having one or more substituents selected from hydroxy and carboxy groups and the structural unit containing the fluorine-containing group, may be fluorine-containing polymer. The hydroxy group may be either an alcoholic hydroxyl group or a phenolic hydroxyl group.

（一般式（３）中の各符号は、前記一般式（１−１）及び前記一般式（１−２）と同様である。）

(Each symbol in the general formula (3) is the same as the general formula (1-1) and the general formula (1-2).)

In the embodiment of the present disclosure, the thermally decomposable fluorine-containing polymer may be a polymer composed of a constituent unit containing a fluorine-containing group, and may be a co-polymer having a constituent unit containing a fluorine-containing group and other constituent units. It may be a polymer. Among them, from the viewpoint of compatibility with other components of the coloring composition, solubility in a solvent, and the like, it is preferable to have other structural units.
When the thermally decomposable fluorine-containing polymer is a copolymer having a constituent unit containing a fluorine-containing group and other constituent units, the copolymer may be a random copolymer, and a fluorine-containing group It may be a block copolymer having a block portion consisting of a structural unit containing a and a block portion consisting of other structural units, and it may be a graft copolymer described later.

As the other constituent unit of the thermally decomposable fluorine-containing polymer, a constituent unit derived from a monomer having an unsaturated double bond can be appropriately selected and used. Examples of the monomer having an unsaturated double bond include (meth) acrylic acid, (meth) acrylic esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, Hexyl (meth) acrylate, chloroethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butoxy ethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isobonyl ( Meta) acrylate, isodexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxy ethylene glycol (meth) acrylate, phenoxyethyl ( Meta) acrylate, stearyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, biphenyloxyethyl acrylate, fluri (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, trimethylolpropane mono (meth) acrylate, polyoxyethylene polyisobutylene monobutyl ether (meth) acrylate of (meth) acrylic acid esters;
(Meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (methacrylamide) (alkyl is methyl, ethyl or propyl), tert-butyl (meth) acrylamide, N-hydroxyethyl-N-methyl (Meth) acrylamides such as (meth) acrylamide, N-2-acetamidoethyl-N-acetyl (meth) acrylamide, etc .;
Allyl esters such as allyl acetate, allyl caproate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and allyl compounds such as allyloxyethanol;
Hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethyl Vinyl ethers such as aminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether;
Vinyl bitylate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl lactate, vinyl β-phenyl And vinyl esters such as butyrate and vinylcyclohexyl carboxylate.

(Graft copolymer)
In the embodiment of the present disclosure, the thermally decomposable fluorine-containing polymer is represented by the general formula (2) from the viewpoints of compatibility with other components of the coloring composition, solubility in a solvent, and the like, among others. It is preferable that it is a graft copolymer which has a structural unit and a structural unit represented by following General formula (4).

（一般式（４）中、Ｌ^４は、直接結合又は２価の連結基、Ｒ^６は、水素原子又はメチル基、Ｐｏｌｙｍｅｒは、下記一般式（５）、下記一般式（６）、及び下記一般式（７）より選択される１種以上を有するポリマー鎖を表す。）

(In the general formula (4), L ⁴ is a direct bond or a divalent linking group, R ⁶ is a hydrogen atom or a methyl group, and Polymer is a compound represented by the following formula (5), the following formula (6), and Represents a polymer chain having one or more selected from the general formula (7))

（一般式（５）中、Ｒ^８は水素原子又はメチル基であり、Ｒ^９は、水素原子、水酸基、ハロゲン原子、シアノ基、炭化水素基、−［ＣＨ（Ｒ^１０）−ＣＨ（Ｒ^１１）−Ｏ］_ｘ１−Ｒ^１２、−［（ＣＨ_２）_ｙ１−Ｏ］_ｚ１−Ｒ^１２、−［ＣＯ−（ＣＨ_２）_ｙ１−Ｏ］_ｚ１−Ｒ^１２、−ＣＯ−Ｏ−Ｒ^１３又は−Ｏ−ＣＯ−Ｒ^１４で示される１価の基、Ｒ^１０及びＲ^１１は、それぞれ独立に水素原子又はメチル基、Ｒ^１２は、水素原子、炭化水素基、−ＣＨＯ、−ＣＨ_２ＣＨＯ又は−ＣＨ_２ＣＯＯＲ^１５で示される１価の基、Ｒ^１３は、炭化水素基、−［ＣＨ（Ｒ^１０）−ＣＨ（Ｒ^１１）−Ｏ］_ｘ２−Ｒ^１２、−［（ＣＨ_２）_ｙ２−Ｏ］_ｚ２−Ｒ^１２、−［ＣＯ−（ＣＨ_２）_ｙ２−Ｏ］_ｚ２−Ｒ^１２で示される１価の基、Ｒ^１４は炭素原子数が１個以上１８個以下の炭化水素基、Ｒ^１５は水素原子又は炭素原子数が１個以上５個以下のアルキル基であり、前記炭化水素基は、置換基を有していてもよい。複数あるＲ^８及びＲ^９は、それぞれ互いに同一であっても異なっていてもよい。
ｎは５以上２００以下の整数を示す。ｘ１及びｘ２は１以上１８以下の整数、ｙ１及びｙ２は１以上５以下の整数、ｚ１及びｚ２は１以上１８以下の整数を示す。
一般式（６）中、ｍ’は１以上５以下の整数、ｎ’は３以上２００以下の整数を示し、複数あるｍ’は互いに同一であっても異なっていてもよい。
一般式（７）中、Ｒ^１６、及びＲ^１７は各々独立に、炭素原子数が２個以上８個以下の直鎖又は分岐のアルキレン基を表し、ｍ”及びｎ”は各々独立に０以上２００以下の整数であり、ｍ”とｎ”の合計は５以上２００以下である。）

(In general formula (5), R ⁸ is a hydrogen atom or a methyl group, R ⁹ is a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a hydrocarbon group,-[CH (R ¹⁰ ) -CH (R ¹¹ ) -O] _{x 1} -R ¹² ,-[(CH ₂ ) _{y 1} -O] _{z 1} -R ¹² ,-[CO- (CH ₂ ) _{y 1} -O] _{z 1} -R ¹² , -CO-O-R ¹³ or- a monovalent group represented by ^{O-CO-R 14, R} 10 and ^{R 11} are each independently hydrogen or ^{methyl, R 12} is a hydrogen atom, a hydrocarbon group, -CHO, _-CH 2 CHO, or - A monovalent group represented by CH ₂ COOR ¹⁵ , R ¹³ is a hydrocarbon group,-[CH (R ¹⁰ ) -CH (R ¹¹ ) -O] _{x 2} -R ¹² ,-[(CH ₂ ) _{y 2} -O ] _z2 -R ^12, _{- [CO-} shown in _{(CH 2) y2 -O] z2} -R 12 A monovalent group, R ¹⁴ is 1 or more 18 or less hydrocarbon groups, R ¹⁵ is a hydrogen atom or one or more 5 or less alkyl group carbon atoms carbon atoms, the hydrocarbon groups And R ⁸ and R ⁹ may be the same or different from each other.
n represents an integer of 5 or more and 200 or less. x1 and x2 are integers of 1 to 18, y1 and y2 are integers of 1 to 5, and z1 and z2 are integers of 1 to 18.
In general formula (6), m 'is an integer of 1 to 5 and n' is an integer of 3 to 200, and a plurality of m's may be the same or different.
In the general formula (7), R ¹⁶ and R ¹⁷ each independently represent a linear or branched alkylene group having 2 to 8 carbon atoms, and m ′ ′ and n ′ ′ each independently represent 0 or more. It is an integer of 200 or less, and the sum of m "and n" is 5 or more and 200 or less. )

Examples of the divalent linking group in L ⁴ include a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, a -CONH- group, a -COO- group, -NHCOO- group, an ether group (-O- group), a thioether group (-S- group), a combination of these, and the like can be mentioned. Among them, L ⁴ is preferably a —COO— group or a divalent linking group containing a —CONH— group.

The hydrocarbon group for R ⁹ , R ¹² , R ¹³ and R ¹⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or It is preferable that it is an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n- group. A butyl group, a tert- butyl group, a cyclopentyl group, a cyclohexyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, a lower alkyl group substituted adamantyl group etc. can be mentioned.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group etc. can be mentioned, for example.
Examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group and the like, which may further have a substituent. The number of carbon atoms in the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less.
Moreover, as said aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenyl methyl group etc. are mentioned, You may have a substituent further. The number of carbon atoms in the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less.
The alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl and Br, and a nitro group.
Moreover, as a substituent of aromatic rings, such as said aryl group and an aralkyl group, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group, a halogen atom, etc. Can be mentioned.
The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.
x1 and x2 are integers of 1 or more and 18 or less, preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, and y1 and y2 are integers of 1 or more and 5 or less, preferably 1 or more and 4 or less It is an integer, more preferably 2 or 3. z1 and z2 are integers of 1 or more and 18 or less, preferably 1 or more and 4 or less, and more preferably 1 or more and 2 or less.
The unit number n of the structural units of the polymer chain may be an integer of 5 to 200, and is not particularly limited, but is preferably in the range of 5 to 100.

In the embodiment of the present disclosure, among them, it is preferable that R ⁹ be —CO—O—R ¹³ from the viewpoint of compatibility with a binder component described later. Specific examples of preferable R ¹³ in the preferable R ⁹ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, chloroethyl group, allyl group and benzyl group , Butoxyethyl group, butoxyethoxy group, cyclohexyl group, dicyclopentanyl group, 2-ethylhexyl group, glycerol group, glycidyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, isobonyl group, isodexyl group, isooctyl group, Lauryl group, 1-adamantyl group, 2-methoxyethyl group, methoxyethoxy group, phenoxyethyl group, stearyl group, dodecyl group, tridecyl group, biphenyloxyethyl group, furfuryl group, tetrahydrofurfuryl group, trimethylolpropyl group, polyoxyethylene Butylene mono butyl group and the like, but not limited thereto.

  In general formula (6), m 'is an integer of 1 or more and 5 or less, preferably an integer of 2 to 5, and more preferably an integer of 4 or 5. The unit number n 'of the structural units of the polymer chain may be an integer of 3 to 200, and is not particularly limited, but is preferably in the range of 5 to 100.

Furthermore, in the general formula (7), R ¹⁶ and R ¹⁷ each independently represent a linear or branched alkylene group having 2 to 8 carbon atoms, and R ¹⁶ and R ¹⁷ have different structures. The Specific examples of R ¹⁶ and R ¹⁷ include ethylene, propylene (trimethylene), methylethylene, butylene (tetramethylene), dimethylethylene, ethylethylene, 1-methylpropylene, pentylene, Examples thereof include a propylethylene group, a hexylene group, a butylethylene group, a heptylene group and an octylene group.
m ′ ′ and n ′ ′ are each independently an integer of 0 or more and 200 or less, and the sum of m ′ ′ and n ′ ′ is 5 or more and 200 or less. When m ′ ′ or n ′ ′ is 0, it indicates that the polymer chain represented by the general formula (7) has a single alkylene group.
The total of m ′ ′ and n ′ ′ may be 5 or more and 200 or less, preferably 5 or more and 50 or less. Even if the repeating unit containing R ¹⁶ and the repeating unit containing R ¹⁷ are random copolymerizations randomly arranged, the repeating unit containing R ¹⁶ and the repeating unit containing R ¹⁷ alternate. It may be a block copolymerization having a block of repeating units containing R ¹⁶ and a block of repeating units containing R ¹⁷ , even if they are arranged alternately.

As a preferable specific example of General formula (7), m ′ ′ is 5 or more, n ′ ′ is 0, R ¹⁶ is a methylethylene group, polypropylene oxide; m ′ ′ is 5 or more, n ′ ′ is 0 ^{There, R 16} is a trimethylene group, polytrimethylene glycol; "at least 5, n" m is ^{0, R 16} is an ethyl ethylene group, polybutylene oxide; at m "is 5 or more, n Ethylene oxide and propylene oxide wherein “is 0, R ¹⁶ is a tetramethylene group; polytetramethylene glycol; m ′ ′ and n ′ ′ are both 1 or more, R ¹⁶ is an ethylene group, and R ¹⁷ is a methyl ethylene group copolymers; m "and n" in both 1 or ^{more, R 16} is a methyl ethylene ^group, propylene oxide and 1,2-butylene oxa Lee ^{R 17} is an ethyl ethylene group Copolymers; at m "and n" are both 1 or more, R ¹⁶ is an ethylene group, R ¹⁷ is a copolymer of ethylene oxide and tetrahydrofuran tetramethylene group.

When it has a polymer chain represented by the general formula (6) or the general formula (7), the end of the polymer chain is not particularly limited. A hydrogen atom or a hydrocarbon group may be mentioned as the end of the polymer chain represented by the general formula (6) or the general formula (7). As a hydrocarbon group which comprises the said terminal, the thing similar to the hydrocarbon group in said R < ⁹ >, R < ¹² >, R <^13> , R < ¹⁴ > is mentioned. In the embodiment of the present disclosure, a hydrogen atom or an alkyl group is particularly preferable as the end of the polymer chain represented by the general formula (6) or the general formula (7), and the number of hydrogen atoms or carbon atoms is 1 or more. Preferred are not more than linear or branched alkyl groups. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.

The mass average molecular weight Mw of the polymer chain in Polymer is preferably in the range of 350 to 20000, and more preferably in the range of 500 to 10000. By being the said range, it is excellent in compatibility with another component.
Further, as a standard, the polymer chain in Polymer preferably has a solubility at 23 ° C. of 50 (g / 100 g solvent) or more with respect to a solvent used in combination.

  When the thermally decomposable fluorine-containing polymer is a copolymer having a structural unit containing a thermally decomposable fluorine-containing group and the other structural units, the proportion of the structural unit containing the thermally decomposable fluorine-containing group is particularly limited Although not preferred, the constituent unit containing a fluorine-containing group is preferably 5% by mass or more and 60% by mass or less, 10% by mass or more and 50% by mass or less, based on the entire constituent unit constituting the thermal decomposition type fluorine-containing polymer It is more preferable that

The mass average molecular weight Mw of the thermally decomposable fluorine-containing polymer is preferably in the range of 1,000 to 100,000, and more preferably in the range of 5,000 to 70,000, from the viewpoint of good compatibility with other resins. preferable. Further, the number average molecular weight Mn of the thermally decomposable fluorine-containing polymer is preferably in the range of 1000 to 50000, and preferably in the range of 1500 to 20000, from the viewpoint of good compatibility with other resins. Is more preferred.
In the present disclosure, the mass average molecular weight Mw and the number average molecular weight Mn are values measured by GPC (gel permeation chromatography). For measurement, using HLC-8220 GPC manufactured by Tosoh Corporation, the elution solvent is N-methylpyrrolidone (NMP) to which 0.01 mol / liter of lithium bromide is added, and the polystyrene standard for calibration curve is Mw: 8 × 10 ⁵ ( F-80), Mw: 4 × 10 ⁵ (F-40), Mw: 2 × 10 ⁵ (F-20), Mw: 1 × 10 ⁵ (F-10), Mw: 4 × 10 ⁴ (F− 4), Mw: 2 × 10 ⁴ (F-2), Mw: 5 × 10 ³ (A-5000), Mw: 2.5 × 10 ³ (A-2500), Mw: 1 × 10 ³ (A− 1000), Mw: 5 × 10 ² (A-500) (all manufactured by Tosoh Corporation), and two measurement columns were used as TSK-GEL ALPHA-M × 2 (manufactured by Tosoh Corporation).

In the present disclosure, a method for confirming that the fluorine-containing polymer is a thermal decomposition-type fluorine-containing polymer from which a fluorine-containing group is separated in a temperature range of 100 ° C. or more and 250 ° C. or less is not particularly limited.
For example, the content of fluorine atoms in the fluorine-containing polymer after heating to 100 ° C., and the content of fluorine atoms in the fluorine-containing polymer after heating to 250 ° C. If the content of fluorine atoms in the fluorine-containing polymer after heating to 250 ° C. is smaller than the content of fluorine atoms in the fluorine-containing polymer after heating up to 100 ° C., 100 ° C. It is confirmed that the polymer is a thermally decomposable fluorine-containing polymer in which a fluorine-containing group is separated in a temperature range of 250 ° C. or less.
The fluorine-containing polymer to be measured is also detected at 100 ° C. or higher by detecting the thermal decomposition product derived from the fluorine-containing group by gas chromatography mass spectrometry (GCMS) in a temperature range of 100 ° C. to 250 ° C. It can be confirmed that the polymer is a thermally decomposable fluorine-containing polymer in which a fluorine-containing group is released in a temperature range of 250 ° C. or lower.
Although the measuring method of content of the fluorine atom in a fluorine-containing polymer is not specifically limited, For example, a fluorescent X ray analysis etc. can be used.

  The content ratio of fluorine atoms after heating to 250 ° C. of the thermally decomposable fluorine-containing polymer is preferably 30% by mass or less, more preferably 10% by mass or less, and 5% by mass or less Is more preferred. If it is below the said upper limit, the wettability of the surface of the obtained colored layer is high, and it is because it is easy to form a coating layer on the surface.

(A) Coloring Material In the coloring composition of the present disclosure, the (A) coloring material includes a salt-forming coloring material of a dye. In the present disclosure, a salt-forming colorant of a dye refers to a dye that is made dispersible by making the dye insoluble in a solvent using a well-known lake formation (chlorination) method, and the dispersibility by the dispersant described later is improved. At the same time, heat resistance and light resistance are also improved. The coloring composition of the present disclosure suppresses the color fading of the color material in the color filter manufacturing process by using the (D) fluorine-containing polymer in combination with the salt-forming coloring material of the dye, and coloring with high brightness You can get a layer.

The dye to be formed can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes and the like.
The salt-forming colorant of the dye can be obtained, for example, by mixing these dyes with a compound having a desired counter ion in a solvent.

  The colored layer formed using the coloring composition of the present disclosure is suitable as a coloring material (A) for enhancing the brightness, since a protective layer and the like can be formed without providing an ultraviolet ray cleaning step. It is preferable to use one containing one or more selected from triarylmethane-based colorants and xanthene-based colorants, in which the luminance is likely to decrease due to ultraviolet irradiation.

The triarylmethane dyes used in the embodiment of the present disclosure can be appropriately selected from known ones, for example, C.I. I. Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 25, 49, 72, C.I. I. Acid Blue 1, 3, 5, 7, 9, 19, 22, 22, 83, 90, 93, 100, 103, 104, 109, C.I. I. Triarylmethane-based acid dyes such as Acid Green 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 18, 22, 50, 50: 1, etc .; I. Basic Violet 1, 3, 14, C.I. I. Basic Blue 1, 5, 7, 8, 11, 26 C.I. I. Basic green 1, 4 etc. triaryl methane series basic dyes, etc. are mentioned.
Moreover, as a xanthene type-dye used and produced by salification, it can select suitably from well-known things, for example, C.I. I. Acid Red 50, 51, 52, 87, 92, 94, 289, 388, C.I. I. Acid violet 9, 30, 102, sulforhodamine G, sulforhodamine B, sulforhodamine 101, sulforhodamine 640 and other xanthene acid dyes; I. Examples thereof include xanthene basic dyes such as Basic Violet 11 and the like.
Among xanthene acid dyes, C.I. I. Acid Red 50, C.I. I. Acid Red 52, C.I. I. Acid Red 289, C.I. I. Acid Violet 9, C.I. I. Acid Violet 30, C.I. I. Rhodamine acid dyes such as Acid Blue 19 are preferred.

  Examples of the counter cation of the salt-forming colorant of the acid dye include metal cations, organic cations, inorganic polymers and the like. As a metal ion, the ion more than bivalence is preferable and calcium ion, barium ion, aluminum ion, copper ion, iron ion etc. are mentioned. The organic cation is not particularly limited, and includes an organic compound containing a functional group capable of forming a salt with an anion such as an amino group, a pyridine group or an imidazole group, and may be colorless or may be a known base Sex dyes may be used. Among them, quaternary ammonium cations and quaternary phosphonium cations are preferred as the organic cation. As the inorganic polymer, polyaluminum chloride or zirconium oxychloride is preferably used.

On the other hand, the counter anion which the salt-forming coloring material of the basic dye has is not particularly limited, and may be an organic anion or an inorganic anion. Specific examples of the organic anion include those described in WO 2012/144520. Further, as the inorganic anion, for example, anions of oxo acids having a valence of 2 or more (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ), etc., or the like And inorganic anions such as polyacid ions in which a plurality of oxo acids are condensed, and mixtures thereof.

  In the present disclosure, xanthene colorants are preferably salt-forming colorants of rhodamine acid dyes, among them, from the viewpoint of being able to form a coating film of high brightness and having excellent heat resistance of colorants, among which The salt-forming coloring material of the rhodamine acid dye of the structure represented by (II) is more preferable.

（一般式（ＩＩ）中、Ｒ^２１〜Ｒ^２４は各々独立に水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表し、Ｒ^２１とＲ^２２、Ｒ^２３とＲ^２４が結合して環構造を形成してもよい。Ｒ^２５は、ハロゲン原子、置換基を有していてもよいアルキル基、スルホナト基（−ＳＯ_３ ⁻基）、又は、カルボキシラト基（−ＣＯＯ⁻基）を表す。ｍは０〜５を表し、Ｒ^２５が複数ある場合、複数あるＲ^２５は互いに同一であっても異なっていてもよい。Ｒ^２６及びＲ^２７は、各々独立に、水素原子、ハロゲン原子、又は置換基を有していてもよいアルキル基を表す。
但し、Ｒ^２１〜Ｒ^２５において、少なくとも２個以上の酸性基又はその塩を有し、そのうち１つは分子内塩を形成する。）

(In the general formula (II), each of R ^{21 to} R ²⁴ independently has a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent R ²¹ and R ²² , and R ²³ and R ²⁴ may combine to form a ring structure, and R ²⁵ is a halogen atom or an alkyl which may have a substituent. group, sulfonato group (-SO ₃ ^- group), or a carboxylato group ^- .m representing the (-COO group) represents 0 to ^{5, when R 25} is plural, a plurality of ^{R 25} are identical to one another R ²⁶ and R ²⁷ each independently represent a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent.
However, R ^{21 to} R ²⁵ have at least two or more acidic groups or salts thereof, and one of them forms an inner salt. )

Examples of the alkyl group in R ^{21 to} R ²⁴ include a linear or branched alkyl group having 1 to 12 carbon atoms, and the like, among which a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. It is more preferable that it is a linear or branched alkyl group having 1 to 5 carbon atoms from the viewpoint of brightness and heat resistance. Among them, the alkyl group in R ^{21 to} R ²⁴ is particularly preferably an ethyl group or a methyl group. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, a substituent containing a sulfonato group (-SO ₃ ^- group), and a carboxylato group (-COO ^- group) And the like. Examples of the substituted alkyl group include a benzyl group and the like, and may further have a sulfonato group or a carboxylato group.
The aryl group in R ^{21 to} R ²⁴ includes, for example, an aryl group having 6 to 12 carbon atoms, and specific examples of the aryl group include, for example, a phenyl group and a naphthyl group. As a substituent which an aryl group may have, an alkyl group, a halogen atom, etc. are mentioned, for example, and the alkyl group may further have a sulfonato group or a carboxylato group.
Examples of the aralkyl group as R ^{21 to} R ²⁴ include aralkyl groups having 7 to 16 carbon atoms, and specific examples include, for example, benzyl group, phenethyl group, naphthylmethyl group, biphenylmethyl group, etc. Furthermore, it may have a sulfonato group or a carboxylato group.

The fact that R ²¹ and R ²² and R ²³ and R ²⁴ combine to form a ring structure means that R ²¹ and R ²² and R ²³ and R ²⁴ form a ring structure via a nitrogen atom. Say The ring structure is not particularly limited, and examples include pyrrolidine ring, piperidine ring, morpholine ring and the like.

The alkyl group in R ²⁶ and R ²⁷ can be the same as the alkyl group in R ^{21 to} R ²⁴ above. ^As the halogen atom in ^{R 26,} and ^{R 27,} a fluorine atom, a chlorine atom, a bromine atom.

R ²⁵ represents a halogen atom, an alkyl group which may have a substituent, a sulfonato group (-SO ₃ ^- group), or a carboxylato group (-COO ^- group). The alkyl group which may have a substituent may be the same as the alkyl group in R ^{21 to} R ²⁴ and may be mentioned, and has a sulfonato group or a carboxylato group. May be
In the general formula (II), the substitution position of the substituent R ²⁵ in the benzene ring bonded to the xanthene skeleton is preferably an ortho position or a para position with respect to the xanthene skeleton from the viewpoint of stability, Is preferred. It is presumed that when the substituent R ²⁵ is in the ortho position, it can resonate with the carbon atom of the xanthene skeleton to which the benzene ring is bonded to form a ring structure, thereby improving the heat resistance.

Among the rhodamine-based acid dyes represented by the above general formula (II), it is a point that the heat resistance is improved that at least one of R ²¹ , R ²² , R ²³ and R ²⁴ is an aryl group or a heteroaryl group It is preferable from In particular, R ²¹ and R ²⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R ²² and R ²³ each independently represent an aryl group or a heteroaryl group However, it is preferable from the point which heat resistance improves. When at least one of R ²¹ , R ²² , R ²³ and R ²⁴ is an aryl group or a heteroaryl group, the nitrogen atom to which at least one of R ²¹ , R ²² , R ²³ and R ²⁴ is bonded is It is presumed that the molecule is more stabilized by resonating not only the xanthene skeleton but also the aryl group or the heteroaryl group.

Specific examples of the acidic group or a salt thereof, a carboxyl group (-COOH), a carboxylato group (-COO ^-), carboxylate (. -COOM, where M is a metal atom), a sulfonato group (-SO ₃ ^-), a sulfo group _(-SO 3 H), sulfonate _(-SO 3 M, wherein M represents a metal atom), and among them, a sulfonato group (-SO ₃ ^-.), a sulfo group it is preferred to have at least one _(-SO 3 H), or sulfonate _(-SO 3 M). In addition, as a metal atom M, a sodium atom, potassium atom, etc. are mentioned.
Rhodamine acid dyes represented by the general formula (II) have at least two acid groups or salts thereof in one molecule in R ^{21 to} R ²⁵ , and one of them forms an inner salt. there, it among others has one acidic group ^{R 25,} preferably has at least one of acidic groups of ^{R 22} and ^{R 23,} an aryl group having at least one acidic group ^{R 22} and ^{R 23} Is more preferred. The presence of the acidic group at a distant position in one molecule is preferable from the viewpoint that the reaction between the acidic group and the cationic species proceeds efficiently.

  Specific examples of the rhodamine acid dyes represented by the general formula (II) include acid red 50, 52, 289, sulforhodamine G, anions of acid violet 9, 30, acid blue 19 and the like, and rhodamine acid Acid Red 52 and 289 are preferable in that they are excellent in the heat resistance of the salt-forming coloring material of the dye, can form a high-brightness coating film, and are easy to obtain.

  As a salt-forming coloring material of the rhodamine-based acid dye, the metal lake color material of the rhodamine-based acid dye described in WO 2015/059962 is excellent in heat resistance and capable of forming a high-brightness coating film. , Particularly preferred.

  Further, in the coloring composition of the present disclosure, the coloring material (A) contains a coloring material represented by the following general formula (I) from the viewpoint of being able to form a coating film having high heat resistance and high brightness. Is preferred.

（一般式（Ｉ）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎが含まれてもよい脂肪族炭化水素基、又は、Ｎと直接結合する末端に脂肪族炭化水素基を有し、炭素鎖中にＯ、Ｓ、Ｎが含まれてもよい芳香族基を表し、
Ｒ^ｉ、Ｒ^ｉｉ、Ｒ^ｉｉｉ、Ｒ^ｉｖ、及びＲ^ｖは各々独立に水素原子、置換基を有してもよいアルキル基又は置換基を有してもよいアリール基を表し、Ｒ^ｉｉとＲ^ｉｉｉ、Ｒ^ｉｖとＲ^ｖが結合して環構造を形成してもよい。
Ｒ^ｖｉ、及びＲ^ｖｉｉは各々独立に置換基を有してもよいアルキル基又は置換基を有してもよいアルコキシ基を表し、
Ａｒ^ｉは置換基を有してもよい２価の芳香族基を表し、
Ｂ^ｃ−は、ｃ価のアニオンを表し、
ａ及びｃは２以上の整数を、ｂ及びｄは１以上の整数を、ｅは０又は１を、ｆ及びｇは０以上４以下の整数を表し、ｆ＋ｅ及びｇ＋ｅは０以上４以下であり、
複数あるＲ^ｉ〜Ｒ^ｖｉｉ、Ａｒ^ｉ、ｅ、ｆ及びｇは、同一であっても異なっていてもよい。）

(In general formula (I), A is an a-valent organic group in which a carbon atom directly bonded to N does not have a π bond, and the organic group is a saturated aliphatic carbon group at the end directly linked to N Aliphatic hydrocarbon group which has a hydrogen group and may contain O, S, N in its carbon chain, or has an aliphatic hydrocarbon group at the end directly bonded to N, and has O in its carbon chain , S and N represent an aromatic group which may be contained,
R ^{i, R ii,} R ^{iii, R iv,} and ^{R v} each independently represent a hydrogen atom, which may have a an optionally substituted alkyl group or a substituted aryl ^{group, R ii} and R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure.
R ^vi and R ^vii each independently represent an alkyl group which may have a substituent or an alkoxy group which may have a substituent,
Ar ⁱ represents a divalent aromatic group which may have a substituent,
B ^c- represents a c-valent anion,
a and c are integers of 2 or more, b and d are integers of 1 or more, e is 0 or 1, f and g are integers of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less ,
Plural R ^{i to} R ^vii , Ar ⁱ , e, f and g may be the same or different. )

In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to N has a linear, branched or cyclic structure if the terminal carbon atom directly bonded to N has no π bond. And any carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and O, S, N are contained in the carbon chain It is also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amido group or the like may be contained, and a hydrogen atom may be further substituted by a halogen atom or the like.
The aromatic group having the above 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 end directly bonded to N at least And may have a substituent, and may be a heterocyclic ring containing O, S and N.
Among them, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group from the viewpoint of backbone fastness.
The cyclic aliphatic hydrocarbon group, cyclohexane, cyclopentane, norbornane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6] decane, include adamantane and the like.
Among them, a bridged alicyclic hydrocarbon group is preferable as the cyclic aliphatic hydrocarbon group from the viewpoint of the fastness of the skeleton. The bridged alicyclic hydrocarbon group is a polycyclic aliphatic hydrocarbon group having a crosslinked structure in an aliphatic ring and having a polycyclic structure, and examples thereof include norbornane and bicyclo [2.2.2]. Octane, tricyclo [5.2.1.0 ^2,6 ] decane, adamantane and the like can be mentioned. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Especially, the group containing a benzene ring is preferable.
From the viewpoint of the availability of raw materials, A is preferably of 2 to 4 valences, more preferably of 2 to 3 valences, and still more preferably of 2 valences. For example, when A is a divalent organic group, a straight-chain, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic having two alkylene groups having 1 to 20 carbon atoms such as xylylene group substituted Group groups and the like.

The alkyl group in R ^{i to} R ^v is not particularly limited. For example, a C1-C20 linear or branched alkyl group etc. are mentioned, It is preferable among them that it is a C1-C8 linear or branched alkyl group, and the carbon atom number is 1 to 6 A linear or branched alkyl group of 5 is more preferable from the viewpoint of easiness of production and raw material procurement. Among them, the alkyl group in R ^{i to} R ^v is particularly preferably an ethyl group or a methyl group. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group and the like, and examples of the substituted alkyl group include a benzyl group and the like.
The aryl group in R ^{i to} R ^v is not particularly limited. For example, a phenyl group, a naphthyl group etc. are mentioned. As a substituent which an aryl group may have, an alkyl group, a halogen atom, etc. are mentioned, for example, As a aryl group which has a substituent, a tolyl group, xylyl group, etc. are preferable.

When at least one of R ^{ii to} R ^v is an aryl group, the heat resistance of the color material is excellent as compared to the case of an alkyl group, but the light resistance tends to be deteriorated. However, in the embodiment of the present disclosure, it is preferable that at least one of R ^{ii to} R ^v be an aryl group in the present embodiment, since the ultraviolet light cleaning step is not necessary in the manufacturing process of the color filter.

The fact that R ⁱⁱ and R ⁱⁱⁱ , and R ^iv and R ^v are combined to form a ring structure means that R ⁱⁱ and R ⁱⁱⁱ , and R ^iv and R ^v are forming a ring structure via a nitrogen atom. Say The ring structure is not particularly limited, and examples include pyrrolidine ring, piperidine ring, morpholine ring and the like.

Among them, from the viewpoint of chemical stability, R ^{i to} R ^v each independently represent 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 Are preferably combined to form a pyrrolidine ring, piperidine ring or morpholine ring.

R ⁱ to R ^v may take the structure are each independently but, among them, it is preferable that in terms of color purity R ⁱ is a hydrogen atom, further R ⁱⁱ ~ in terms of manufacturing and ease of procurement of raw materials More preferably, R ^v is all the same or R ⁱⁱ and R ^v are the same and R ⁱⁱⁱ and R ^iv are the same.

Each of R ^{vi to} R ^vii independently represents an alkyl group which may have a substituent or an alkoxy group which may have a substituent. The alkyl group in R ^{vi to} R ^vii is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and is an alkyl having 1 to 4 carbon atoms. More preferred is a group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group, which may be linear or may have a branch.
The alkoxy group in R ^{vi to} R ^vii is not particularly limited, but is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, and 1 to 4 carbon atoms. More preferably, it is an alkoxy group of Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, which may be linear or may have a branch.
The substitution number of R ^{vi to} R ^vii , that is, f and g each independently represent an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less, and more preferably 0 or more and 1 or less.
Further, R ^{vi to} R ^vii may be substituted at any position of the aromatic ring having a resonance structure in the triarylmethane skeleton or the xanthene skeleton, but among them, -NR ⁱⁱ R ⁱⁱⁱ or -NR ^iv It is preferable that the meta position is substituted based on the amino group represented by R ^v .

The divalent aromatic group in Ar ⁱ is not particularly limited. The aromatic group may be a heterocyclic group in addition to an aromatic hydrocarbon group consisting of carbon rings. As the aromatic hydrocarbon in the aromatic hydrocarbon group, fused polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring and the like other than benzene ring; biphenyl, terphenyl, And chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane and stilbene. The chained polycyclic hydrocarbon may have O, S, and N in the chain skeleton as in diphenyl ether and the like. On the other hand, as the heterocyclic ring in the heterocyclic group, 5-membered heterocyclic rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; 6-membered heterocyclic rings such as pyrane, pyrone, pyridine, pyrone, pyridazine, pyrimidine and pyrazine And fused polycyclic heterocyclic rings such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like. As these aromatic groups substituents, in the R ^vi to R ^vii, it may have an alkoxy group which may have an alkyl group or a substituent which may have a substituent.

The divalent or higher anion (B ^{c −} ) is not particularly limited, and may be an organic anion or an inorganic anion. As these anions, the thing similar to the counter anion which the salt-forming coloring material of the said basic dye has can be selected suitably, and can be used.
In the embodiment of the present disclosure, the divalent or higher anion is preferably a polyacid anion containing at least one of tungsten and molybdenum among them, from the viewpoint of heat resistance and light resistance of the coloring material, and a polyacid containing tungsten among others It is more preferable that it is an anion. A coloring material having a polyacid anion containing tungsten is particularly excellent in heat resistance, but tends to be deteriorated in light resistance. However, since the embodiment of the present disclosure does not require the ultraviolet light cleaning step in the manufacturing process of the color filter, it is preferable to use a polyacid anion containing tungsten which is excellent in heat resistance in this embodiment.

Specific examples of the polyacid anion containing at least one of tungsten and molybdenum include, for example, Keggin-type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ , Dawson-type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin type silicotungstic acid ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , and further, [P ₂ W ₁₇ O ₆₁ ] ^10- as another example, [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ ] ^{_{W 30 O 110] 14-, α-}} [SiW 9 O 34] 10-, γ- [SiW 10 O 36] 8-, α- [SiW 11 O 39] 8-, β- [SiW ^{_{1 O 39] 8-, [W}} 6 O 19] 2-, [W 10 O 32] 4-, WO 4 2-, α- [PMo 12 O 40] 3-, α- [PW 11 MoO 40] 3 ⁻ , Α- [PW ₉ Mo ₃ O ₄₀ ] ³⁻ , α- [PW ₃ Mo ₉ O ₄₀ ] ³⁻ , α- [SiMo ₁₂ O ₄₀ ] ⁴⁻ , α- [P ₂ Mo ₁₈ O ₆₂ ] ^{6 _{-, [Mo 2 O 7]}} 2-, [Mo 6 O 19] 2-, include _{[Mo 8 O} ^{26] 4-,} and the like.
Among the anions of inorganic acids containing molybdenum and / or tungsten, heteropoly acids are preferable among the above from the viewpoints of heat resistance and light resistance and availability of raw materials, and further P (phosphorus) is included. More preferably, it is a heteropoly acid.

(Other color materials)
In the embodiment of the present disclosure, the coloring composition may further contain other coloring materials as long as the effects are not impaired. Other coloring materials are blended as needed for the purpose of control of color tone. In the coloring composition of the present embodiment, the other coloring materials are not particularly limited as long as they can be colored as desired when forming the coloring layer, and various organic pigments, inorganic pigments, dyes and the like are not particularly limited. It can be used alone or in combination of two or more. Among them, organic pigments are preferably used because they have high color developability and high heat resistance. As the organic pigment, for example, compounds classified into Pigment in Color Index (CI; published by The Society of Dyers and Colourists), specifically, Color Index (C. I as shown below) .) Can be mentioned.

Examples of other coloring materials include, but are not limited to, the following.
C. 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 pigment red 82 and dyes such as acid red.

  The blending amount of the other coloring materials is preferably 40 parts by mass or less, and more preferably 20 parts by mass or less based on 100 parts by mass of the total amount of the coloring material (A). Within this range, it is possible to control the color tone without impairing the characteristics of the high transmittance of the salt-forming coloring material of the dye.

(B) Dispersant In the coloring composition of the present disclosure, the colorant is used by being dispersed in a solvent by a dispersant. As a dispersing agent, it can select suitably from what is conventionally used as a dispersing agent, and can be used. As a specific example of a dispersing agent, surfactant, such as cationic type, anionic type, nonionic type, amphoteric, silicone type, a fluorine type, can be used, for example. Among the surfactants, polymer surfactants (polymer dispersants) are preferable in that they can be dispersed uniformly and finely. These dispersants may be used alone or in combination of two or more.

  As the polymer dispersant, for example, (co) polymers of unsaturated carboxylic acid ester such as polyacrylic acid ester; (partial) amine salt of (co) polymer of unsaturated carboxylic acid such as polyacrylic acid (Partially) ammonium salts and (partially) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and modified products thereof; polyurethanes; unsaturated polyamides; Long-chain polyamino amide phosphates; Polyethylenimine derivatives (amides obtained by reaction of poly (lower alkylenimine) with free carboxyl group-containing polyesters and their bases); Polyallylamine derivatives (polyallylamine and free carboxyls) Co-Condensation of Polyester, Polyamide or Ester Having a Group The reaction product obtained by reacting one or more compound selected from among the three compounds of (polyester amide)), and the like.

As a commercial item of such a dispersing agent, for example, Disperbyk-2000, 2001, BYK-LPN6919, 21116 (all, manufactured by Big Chemie Japan),
Addisper PB 821, 881 (manufactured by Ajinomoto Co., Ltd.) and the like can be mentioned. Among them, BYK-LPN 6919 and 21116 are preferable in terms of heat resistance, electrical reliability, and dispersibility.

Among them, as the polymer dispersant, a polymer having at least a constitutional unit represented by the following general formula (III) from the viewpoint of being able to suitably disperse the above-mentioned coloring material and having good dispersion stability, 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 1 or more urethane bond (-NH-COO-) in a molecule | numerator.
The above-mentioned preferable dispersants will be described in detail below.

<Polymer Having at least a Structural Unit Represented by the Following General Formula (III)>
In the embodiment of the present disclosure, a polymer having at least a constituent unit represented by the following general formula (III) can be suitably used as a dispersant.

（一般式（ＩＩＩ）中、Ｒ^３１は、水素原子又はメチル基、Ｌ^５は、直接結合又は２価の連結基、Ｑ^２は、下記一般式（ＩＩＩ−ａ）で表される基、又は、置換基を有していても良い、塩形成可能な含窒素複素環基を表す。）

(In the general formula (III), R ³¹ is a hydrogen atom or a methyl group, L ⁵ is a direct bond or a divalent linking group, and Q ² is a group represented by the following general formula (III-a), or Represents a saltable nitrogen-containing heterocyclic group which may have a substituent.)

（一般式（ＩＩＩ−ａ）中、Ｒ^３２及びＲ^３３は、それぞれ独立して、水素原子又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^３２及びＲ^３３は互いに同一であっても異なっていても良い。）

(In general formula (III-a), R ³² and R ³³ each independently represent a hydrogen atom or a hydrocarbon group which may contain a hetero atom, and R ³² and R ³³ are the same or different from each other May be

In the general formula (III), L ⁵ is a direct bond or a divalent linking group. Direct bonding means that Q ² is directly bonded to a carbon atom in the general formula (III) without a linking group.
Examples of the divalent linking group for L ⁵ include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (-R'- OR "-: R 'and R" each independently represent an alkylene group), a combination thereof and the like.
Among them, from the viewpoint of dispersibility, L ⁵ in the general formula (III) is preferably a direct bond, a -CONH- group, or a divalent linking group containing a -COO- group.

  Moreover, it can be especially suitably used by carrying out the salt formation of the structural unit represented by the said General formula (III) of these dispersing agents by the following salt formation agent in arbitrary ratios.

Among the polymers having a structural unit represented by the general formula (III), among them, WO 2011/108495, JP-A 2013-054200, JP-A 2010-237608, and JP-A 2011-75661 Block copolymer having the structure described in the above, and graft copolymer improve the dispersibility and dispersion stability of the color material and the heat resistance of the resin composition, and can form a high brightness and high contrast colored layer It is preferable from
Moreover, BYK-LPN6919 etc. are mentioned as a commercial item of the polymer which has a structural unit represented by General formula (III).

«Salt forming agent»
A preferable dispersant in the embodiment of the present disclosure is a polymer in which at least a part of the nitrogen moiety of the constituent unit represented by the above general formula (III) has formed a salt (hereinafter may be referred to as salt modification). It is.
In the present invention, the salt forming agent is used to salt the nitrogen moiety of the constituent unit represented by the general formula (III), thereby strongly adsorbing the dispersant to the coloring material similarly forming a salt. By doing this, the dispersibility and dispersion stability of the coloring material are improved. As a salt formation agent, the acidic organophosphorus compound of WO2011 / 108495, Unexamined-Japanese-Patent No. 2013-054200, an organic sulfonic acid compound, a quaternizing agent etc. can be used conveniently. In particular, when the salt forming agent is an acidic organic phosphorus compound, the coloring material surface is phosphated by the localization of the salt formation site containing the acidic organic phosphorus compound of the dispersing agent on the particle surface of the coloring material. As a result of being in a coated state, attack (hydrogen abstraction) on the dye skeleton of the coloring material by active oxygen 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-denatured with an acidic organic phosphorus compound is used as a dispersant, color fading at the time of high temperature heating can be further suppressed in a state where the high transmittance color material used in the present invention is well dispersed. Even after the high temperature heating step in the filter manufacturing step, a colored layer with higher brightness can be formed.

<Urethane-based dispersant>
The urethane type dispersing agent suitably used as a dispersing agent is a dispersing agent which consists of a compound which has one or more urethane bond (-NH-COO-) in 1 molecule.
By using a urethane dispersant, good dispersion can be achieved with a small amount. By setting the amount of the dispersing agent to a small amount, it is possible to relatively increase the compounding amount of the curing component and the like, and as a result, it is possible to form a colored layer excellent in heat resistance.

  In the present disclosure, as the urethane dispersant, among them, (1) polyisocyanate having two or more isocyanate groups in one molecule, (2) polyester having a hydroxyl group at one end or both ends, and one end or one end 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 And (2) at least one selected from polyesters having a hydroxyl group at one end or both ends, and poly (meth) acrylates having a hydroxyl group at one end or both ends, and (3) active hydrogen in the same molecule More preferably, it is a reaction product of a compound having a basic group or an acidic group.

  Commercially available urethane dispersants include Disperbyk-161, 162, 163, 164, 167, 168, 170, 171, 174, 182, 183, 184, 185, BYK-9077 (all manufactured by Big Chemie Japan), Addispur PB711 (manufactured by Ajinomoto Co., Ltd.), EFKA-46, 47, 48 (manufactured by EFKA CHEMICALS), and the like can be mentioned. Among them, Disperbyk-161, 162, 166, 170, and 174 are preferable in terms of heat resistance, electrical reliability, and dispersibility.

In the coloring composition of the present disclosure, the content of the (B) dispersant is not particularly limited as long as the (A) coloring material can be uniformly dispersed, but the (A) coloring material is not particularly limited. Is preferably 1% by mass or more, and more preferably 5% by mass or more based on the total solid content of the coloring composition, from the viewpoint of excellent dispersibility and dispersion stability of the above and storage stability. . In addition, the content of the dispersant (B) is preferably 50% by mass or less, and 40% by mass or less based on the total solid content of the coloring composition, from the viewpoint of achieving good developability. Is more preferable, and 30% by mass or less is even more preferable.
In addition, a dispersing agent can be used individually by 1 type or in combination of 2 or more types.

(C) Binder Component The colored composition of the present disclosure contains a binder component to impart film formability and adhesion to a surface to be coated. Among them, in order to impart sufficient hardness to the coating film, it is preferable to contain a curable binder component. The curable binder component is not particularly limited, and a curable binder component used to form a colored layer of a conventionally known color filter can be appropriately used.
As the curable binder component, for example, a photocurable binder component containing a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam or the like, or a thermosetting resin that can be polymerized and cured by heating What contains the thermosetting binder component which can be used can be used.

When the colored composition of the present disclosure can be selectively attached 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 to have developability. In this case, a known thermosetting binder component, a photosensitive binder component, and the like used when forming a color filter colored layer by an inkjet method or the like can be appropriately used.
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 further added. As a thermosetting functional group, an epoxy group, oxetanyl group, an isocyanate group, an ethylenically unsaturated bond, etc. are mentioned. An epoxy group is preferably used as the thermosetting functional group. As a specific example of a thermosetting binder component, the thing as described in international publication 2012/144521 can be mentioned, for example.

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 a 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 including an alkali-soluble resin and an o-quinonediazide group-containing compound as a photosensitivity imparting 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 suitably used.
The coloring composition of the present disclosure is preferably a negative photosensitive binder component from the viewpoint that a pattern can be easily formed by photolithography using an existing process.
The alkali-soluble resin, the polyfunctional monomer, and the photoinitiator, which constitute the negative photosensitive binder component, will be specifically described below.

(1) Alkali-Soluble Resin In the embodiment of the present disclosure, the alkali-soluble resin has an acidic group, acts as a binder resin, and is soluble in a developer used when forming a pattern, particularly preferably an alkaline developer. As long as it exists, it can be selected appropriately and used.
The preferred alkali-soluble resin in the embodiment of the present disclosure is a resin having a carboxyl group as an acidic group. Specifically, an acrylic copolymer having a carboxyl group, an epoxy (meth) acrylate having a carboxyl group Resin etc. are 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. It is because the film strength of the cured film formed by containing a photopolymerizable functional group is improved. In addition, 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 carbon ring. The aromatic carbon ring functions as a component that imparts coating properties to the coloring 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 the alkali solubility of the coloring composition, but also functions as a component that improves the solubility in a solvent and the solvent resolubility.

Specific examples of the acrylic copolymer having a carboxyl group include, for example, those described in WO 2012/144521, and specifically, for example, methyl (meth) acrylate, ethyl ( The copolymer which consists of a monomer which does not have carboxyl groups, such as a meta) acrylate, and 1 or more types chosen from (meth) acrylic acid and its anhydride can be illustrated. In addition, for example, polymers in which an ethylenically unsaturated bond is introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above-mentioned copolymer can be exemplified, but the present invention is limited thereto It is not something to be done.
Among these, polymers or the like into which an ethylenically unsaturated bond is introduced by addition of an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to a copolymer are polymerized with a polyfunctional monomer described later at the time of exposure. Is particularly preferable in that the colored layer is 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, if the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the obtained coating film in an alkali developer decreases, and pattern formation becomes difficult. On the other hand, if the copolymerization ratio exceeds 50% by mass, the formed pattern may tend to come off from the substrate or to roughen the surface of the pattern during development with an alkaline developer.

  The preferable mass average molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 500,000, and more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is significantly reduced, and if it exceeds 500,000, pattern formation may be difficult at the time of development with an alkali developer. The mass average molecular weight is determined by gel permeation chromatography (GPC) as a standard polystyrene equivalent value.

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, but an epoxy (meth) obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones and used. As a specific example, the thing etc. which are described in international publication 2012/144521 gazette are mentioned, for example. The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride may be used alone or in combination of two or more.

  The alkali-soluble resin used in the embodiment of the present disclosure may be used singly or in combination of two or more, and the content thereof is 100 mass parts of the coloring material contained in the coloring composition. The amount 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. 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 proportion of the coloring material becomes relatively low, which is sufficient. In some cases, the color density can not be obtained.

(2) Polyfunctional Monomer The polyfunctional monomer used in the embodiment of the present disclosure is not particularly limited as long as it can be polymerized by a photoinitiator to be described later, and usually 2 ethylenically unsaturated double bonds are used. It is preferable that it is a polyfunctional (meth) acrylate in which the compound which has three or more is used and it has especially 2 or more of acryloyl group or methacryloyl groups.
As such a polyfunctional (meth) acrylate, it may select suitably from conventionally well-known things, and may be used. As a specific example, the thing etc. which are described in international publication 2012/144521 gazette are mentioned, for example.

  One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. Moreover, when excellent photocurability (high sensitivity) is required for the coloring composition of the present disclosure, the polyfunctional monomer has three or more polymerizable double bonds (trifunctional) or more. Are preferred, and poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid derivatives are preferred. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentamer are preferable. Succinic acid modification of erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid modification of dipentaerythritol penta (meth) acrylate Products, dipentaerythritol hexa ( ) Acrylate, tris (2- (meth) acryloyloxyethyl) phosphate, tris (2- (meth) allyl acryloyloxy propyl) phosphate and the like as preferred.

  The total content of the polyfunctional monomer used in the coloring composition of the present disclosure is not particularly limited, but generally about 5 to 500 parts by mass, preferably 20 to 300 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. The scope of the department. If the content of the polyfunctional monomer is less than the above range, light curing may not proceed sufficiently, and the exposed portion may elute. If the content of the polyfunctional monomer is more than the above range, the alkali developability may be reduced. There is.

(3) Photoinitiator There is no restriction | limiting in particular as a photoinitiator used in the coloring composition of this indication, It is used combining 1 type, or 2 or more types out of conventionally known various photoinitiators. Can. As a specific example, the thing etc. which are described in international publication 2012/144521 gazette are mentioned, for example.

  The content of the photoinitiator used in the coloring composition of the present disclosure is usually about 0.01 to 100 parts by mass, preferably 5 to 60 parts by mass, with respect to 100 parts by mass of the polyfunctional monomer. If this content is less than the above range, a sufficient polymerization reaction can not be generated, and therefore the hardness of the colored layer may not be sufficient. On the other hand, if it is more than the above range, the solid content of the colored composition is The content of the coloring material and the like in the minute may be relatively reduced, and a sufficient coloring density may not be obtained.

(E) Solvent In the embodiment of the present disclosure, the solvent does not react with each component in the coloring composition, and can be appropriately selected and used from solvents which can dissolve or disperse these. Specifically, alcohol type; ether alcohol type; ester type; ketone type; ether alcohol acetate type; ether type; aprotic amide type; lactone type; unsaturated hydrocarbon type; organic solvent such as saturated hydrocarbon type Among them, it is preferable to use an ester solvent from the viewpoint of solubility at the time of 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, Diethylene glycol monobutyl ether acetate etc. are mentioned.
Above all, it is preferable to use propylene glycol monomethyl ether acetate (PGMEA) from the viewpoints of low danger to human body and low volatility at around room temperature but good heat drying property. In this case, there is an advantage that a special cleaning step is not required even when switching to a coloring composition using conventional PGMEA.
These solvents may be used alone or in combination of two or more.

(Optional additives)
In the embodiment of the present disclosure, various additives may be included as needed as long as the purpose is not impaired.
Examples of the additive include an antioxidant, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet light absorber, an adhesion promoter and the like.
Specific examples of the surfactant and the plasticizer include, for example, those described in WO 2012/144521.

It is preferable from the viewpoint of heat resistance and light resistance that the coloring composition further contains an antioxidant. The antioxidant may be appropriately selected from those known in the art. Specific examples of the antioxidant include, for example, hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc. From the point of view, it is preferable to use a hindered phenolic antioxidant.
A hindered phenolic antioxidant contains at least one phenol structure, and a structure in which at least one of the 2- and 6-positions of hydroxyl groups of the phenol structure is substituted with a substituent having 4 or more carbon atoms It means the antioxidant which it has. In addition, the latent antioxidant may be a latent antioxidant in which a hindered phenolic hydroxyl group is protected by a protecting group as described in JP-A-2015-132791.

(Blending ratio of each component in the coloring composition)
The total content of (A) coloring materials including salt forming coloring materials of dyes and other coloring materials is 5 to 65% by mass, more preferably 8 to 55% by mass with respect to the total solid content of the coloring composition It is preferable to blend in the ratio of If the amount of the coloring material is too small, the transmission density may be insufficient when the coloring composition is applied to a predetermined thickness (usually 1.0 to 5.0 μm). When the composition is applied onto a substrate and cured, the adhesion to the substrate, the surface roughness of the cured film, the coating film hardness, etc. may become insufficient, and the colored composition may be insufficient. Since the proportion of the amount of the dispersant used to disperse the coloring material is also increased, there is a possibility that the properties such as solvent resistance may become insufficient. In the present disclosure, the solid content is all components other than the above-described solvents, and includes polyfunctional monomers and the like dissolved in the solvent.
The content of the dispersant (B) is not particularly limited as long as the colorant can be uniformly dispersed, and for example, 10 to 150 parts by mass with respect to 100 parts by mass of the colorant be able to. Furthermore, it is preferable to mix | blend in the ratio of 15-100 mass parts with respect to 100 mass parts of coloring materials, and it is preferable to mix | blend in the ratio of 15-70 mass parts especially. The total content of the dispersant is preferably in the range of 1 to 60% by mass, and more preferably in the range of 5 to 50% by mass, with respect to the total solid content of the coloring composition. If the content is less than 1% by mass with respect to the total solid content of the coloring composition, it may be difficult to uniformly disperse the coloring material, and if it exceeds 60% by mass, There is a possibility that curability and developability may be reduced.
The total amount of the binder component (C) is preferably 5 to 90% by mass, preferably 10 to 80% by mass, based on the total solid content of the coloring composition.
The content of the (D) fluorine-containing polymer is preferably 0.01 to 1% by mass, and preferably 0.05 to 0.5% by mass, based on the total solid content of the coloring composition.
Further, the content of the solvent (E) is not particularly limited as long as the colored layer can be formed with high accuracy. It is preferably in the range of 65 to 95% by mass, and more preferably in the range of 75 to 88% by mass, based on the total amount of the coloring composition containing the solvent. When the content of the solvent is in the above range, the coating property can be excellent.

(Production of coloring composition)
As a method for producing a coloring composition, for example, first, a coloring material dispersion liquid containing at least (A) a coloring material, (B) a dispersing agent, and (E) a solvent is prepared, and the coloring material A method of simultaneously charging and mixing the dispersion, (C) binder component, (D) fluorine-containing compound, and various additive components optionally used, (2) in the solvent (C) binder component, (D) The fluorine-containing compound and various additive components optionally used may be added and mixed, and then the colorant dispersion may be added and mixed.
In addition, the colorant dispersion is prepared by mixing (B) the dispersant in (E) solvent and stirring to prepare a dispersant solution, and then the dispersant solution, (A) the colorant and optionally others. These compounds can be prepared by mixing and dispersing using a disperser. Alternatively, the colorant and the dispersant may be mixed in a solvent and dispersed by using a known disperser.

  Examples of dispersers for dispersing colorants include roll mills such as two rolls and three rolls, ball mills such as ball mills and vibratory ball mills, paint conditioners, bead mills such as continuous disc type bead mills and continuous annular type bead mills. Be As a preferable dispersion condition of a bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, more preferably 0.05 to 1.0 mm.

  Specifically, preliminary dispersion is performed using 2 mm zirconia beads having relatively large bead diameters, and further, main dispersion using 0.1 mm zirconia beads having relatively small bead diameters is mentioned. Moreover, it is preferable to filter with a 0.1-2.0 micrometers membrane filter after dispersion | distribution.

2. Color Filter A color filter according to an embodiment of the present disclosure is a color filter having a colored layer on a transparent substrate, and at least one of the colored layers is a cured product of the colored composition of the present embodiment.

A color filter according to such an embodiment of the present disclosure will be described with reference to the drawings. 1 and 2 are each a schematic cross-sectional view showing an embodiment of a color filter. The color filter 10 shown in the example of FIG. 1 includes a transparent substrate 1, a light shielding portion 2, and a colored layer 3. Further, the color filter 10 shown in the example of FIG. 2 includes the transparent substrate 1, the light shielding portion 2, and the colored layer 3, and further includes the covering layer 4 on the colored layer 3.
The color filter of the present disclosure has a colored layer having high brightness, high smoothness, and excellent surface wettability because at least one of the colored layers is a cured product of the colored composition of the present disclosure. doing. Moreover, when it has a coating layer, it becomes a color filter by which the coating-film nonuniformity of the said coating layer was suppressed.

(Colored layer)
In the color filter according to the embodiment of the present disclosure, at least one of the colored layers is a cured product of the coloring composition of the present embodiment.
The colored layer is usually formed at an opening of a light shielding portion on a transparent substrate described later, and is usually formed of a coloring pattern of three or more colors.
Moreover, it does not specifically limit as arrangement | sequence of the said colored layer, For example, it can be set as general arrangement, such as stripe type, mosaic type, triangle type, 4 pixel arrangement | positioning type | mold. In addition, the width, area, and the like of the colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration of the colored composition, the viscosity and the like, but in general, the range of 1 to 5 μm is preferable.

(Light blocking part)
The color filter according to the embodiment of the present disclosure may have a light shielding portion. The light shielding portion is formed in a pattern on a transparent substrate to be described later, and can be the same as that used as a light shielding portion in a general color filter.
It does not specifically limit as a pattern shape of the said light-shielding part, For example, shapes, such as stripe form and a matrix form, are mentioned. 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, CrO _x film (x is an arbitrary number) may be one and the Cr film is two-layered, also, CrO _x film (x is an arbitrary number) with reduced more reflectivity Alternatively, three layers of CrN _y films (y is an arbitrary number) and Cr films may be stacked.
When the light shielding portion is obtained by dispersing or dissolving a black color material in a binder resin, a method of forming the light shielding portion is not particularly limited as long as the light shielding portion can be patterned. For example, the photolithography method, the printing method, the inkjet method etc. using the coloring resin composition for light-shielding parts can be mentioned.

  The film thickness of the light shielding portion is set to about 0.2 to 0.4 μm in the case of a metal thin film, and in the case of about 0.5 to 2 μm in the case where a black color material is dispersed or dissolved in a binder resin. It is set.

(Transparent substrate)
The transparent substrate in the color filter according to the embodiment of the present disclosure is not particularly limited as long as it is a transparent substrate to visible light, and a transparent substrate used for a general color filter can be used. . Specifically, it has flexibility and flexibility such as transparent non-flexible rigid material such as quartz glass, non-alkali glass, synthetic quartz plate, or transparent resin film, resin plate for optics, flexible glass, etc. 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, a thing about 50 micrometers-about 1 mm can be used, for example.
In the color filter of the present invention, besides the transparent substrate, the light shielding portion and the colored layer, for example, an overcoat layer, a transparent electrode layer, an alignment film for aligning a liquid crystal material, and columnar spacers are formed. It may be done. The color filter of the present disclosure is not limited to the configuration exemplified above, and a known configuration generally used for the color filter can be appropriately selected and used.

(Cover layer)
The color filter according to the embodiment of the present disclosure may optionally have a covering layer on the colored layer. The coating layer in the present embodiment is not particularly limited, and may be appropriately selected from various layers or films which can be generally provided on the colored layer, as necessary. Examples of the covering layer include, in addition to a protective layer for protecting the colored layer, an alignment film (alignment layer) and a transparent conductive layer such as an ITO film.
In the color filter of the present embodiment, since at least one of the colored layers is a cured product of the colored composition of the present disclosure, any covering layer can be a uniform covering layer.

When the covering layer is a protective layer, the protective layer may be a layer transparent to visible light, and can be appropriately selected from organic protective layers used for general color filters, and contains a resin It is preferably a protective layer.
The resin for the protective layer may be appropriately selected from conventionally known ones, and may be a thermoplastic resin, or a cured product of a thermosetting resin or a photocurable resin.
Although the formation method of a protective layer is not specifically limited, It is preferable to use the following composition for protective layers. As described above, in the colored layer formed using the coloring composition of the present disclosure, the acidic group or hydroxyl group after the removal of the fluorine-containing group from the above-mentioned fluorine-containing polymer tends to be easily exposed to the surface. Therefore, the surface of the colored layer has high hydrophilicity and lipophilicity, and the composition for protective layer can be applied uniformly.
In addition, when forming a protective layer as a coating layer in this embodiment, you may provide the said orientation film, the said transparent conductive layer, etc. on the said protective layer.
In addition, in the present embodiment, a transparent conductive layer may be provided as a covering layer adjacent to the colored layer.

<Composition for Protective Layer>
The composition for a protective layer contains at least a resin to be a protective layer, usually contains a solvent, and may further contain other components as necessary.
As resin contained in the composition for protective layers, what is generally used as a transparent protective layer of a color filter can be used, It is a thermosetting composition even if it is a photocurable composition. Good. As a photocurable composition, the composition containing the said polyfunctional monomer and the said photoinitiator is mentioned, Furthermore, an acrylic resin, a styrene resin, novolak resin, maleic acid resin, rosin resin etc. are mentioned. It may contain a binder resin.

On the other hand, in the embodiment of the present disclosure, among them, a thermosetting composition is preferable in that the number of times of light irradiation can be reduced.
As the thermosetting composition, a combination of a compound having a thermosetting functional group and a curing agent is usually used, and a catalyst which accelerates the thermosetting reaction may be further added, and further, a thermosetting functional group and It may further contain other resin components that may or may not react.

In the embodiment of the present disclosure, as described above, since the acidic group and the hydroxyl group tend to be easily exposed on the surface of the colored layer, as a compound having a thermosetting functional group from the viewpoint of excellent adhesion with the colored layer. It is preferable to use a compound having an epoxy group.
The compound having an epoxy group preferably contains an epoxy compound having two or more epoxy groups in one molecule. An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more epoxy groups, preferably 2 to 50, more preferably 2 to 20 in one molecule (referred to as epoxy resin Including those). The epoxy group should just be a structure which has an oxirane ring structure, for example, can show a glycidyl group, an epoxy cyclohexyl group, etc. As an epoxy compound, the well-known polyvalent epoxy compound which can be hardened with carboxylic acid can be mentioned, for example, such an epoxy compound is "Made of Shinhobo""Epoxy resin handbook" Nikkan Kogyo Shimbun Co., Ltd. (Showa 62) Etc., and it is possible to use these.

As the above-mentioned epoxy compound, for example, a polymer containing a monomer containing an epoxy group such as glycidyl (meth) acrylate is suitably mentioned, and a copolymer with another monomer not having an epoxy group It may be.
Moreover, as an epoxy compound called an epoxy resin, what contains 2 or more of epoxy groups in one molecule is preferable, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin Bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, ortho cresol novolac type epoxy resin, trishydroxyphenylmethane type Epoxy resin, trifunctional epoxy resin, tetraphenylol ethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphe Lumpur A 含核 polyol type epoxy resins, polypropylene glycol type epoxy resins, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.

  As a curing agent used for a thermosetting composition, it can select suitably from well-known curing agents, and can use it. Examples of the curing agent include amines, imidazoles, polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and polyvalent carboxylic acids in which a carboxyl group is blocked.

The other resin component is a component contained for the purpose of improving the heat resistance, scratch resistance and the like of the protective layer, and can be appropriately selected from conventionally known ones. For example, polyester amic acid obtained by reacting tetracarboxylic acid dianhydride, diamine and a high hydroxyl compound, or organosilane condensate (organic-inorganic hybrid type) can be used.
In addition, the composition for a protective layer may further contain known additives such as an antioxidant, a leveling agent, a silane coupling agent, and a chain transfer agent, as necessary.

The alignment film used as the covering layer is a layer for aligning the liquid crystal compound in a certain direction. In the present embodiment, the alignment film is preferably formed using a composition for alignment film.
The composition for alignment film can be appropriately selected and used from conventionally known ones. For example, compositions for silane coupling-based alignment films such as lecithin, silane-based surfactants, titanate-based surfactants, pyridinium salt-based polymeric surfactants, n-octadecyltriethoxysilane, long-chain alkyl groups and alicyclic resins The composition for polyimide-type alignment films, such as a soluble polyimide which has a formula structure in a side chain, and a polyamic acid which has a long chain alkyl group and an alicyclic structure in a side chain, is applicable.

3. Method of Manufacturing Color Filter A method of manufacturing a color filter according to an embodiment of the present disclosure is a method of manufacturing a color filter having a colored layer on a transparent substrate,
A step (i) of forming a coating film of the coloring composition of the present embodiment on a transparent substrate;
Curing the coating (ii);
And a step (iii) of heating the cured coating.

Since the method for producing a color filter uses the colored composition of the present embodiment, it is possible to improve the surface wettability without irradiating the cured coating film of the colored composition with ultraviolet light. As a result, it is possible to manufacture a color filter in which the decrease in luminance of the colored layer is suppressed.
The production method of the present disclosure comprises at least the above step (i) to step (iii), and further optionally, a step (iv) of forming a covering layer on the colored layer, or the above-mentioned method It may have the process of providing the said light-shielding part beforehand on a transparent substrate. Hereinafter, each step will be described, but each component in the coloring composition and each configuration of the color filter are as described above, and therefore the description thereof is omitted here.

(Step (i))
The formation method of the coating film of the coloring composition which concerns on the said embodiment is not specifically limited, It can be set as the method similar to the manufacturing method of a general color filter. For example, it apply | coats on a transparent substrate using coating means, such as a spray coat method, a dip coat method, a bar coat method, a roll coat method, a spin coat method, and forms a wet coating film. Then, it is dried by a known means such as heating if necessary to remove the solvent in the coloring composition.

(Step (ii))
The step of curing the coating film obtained in the step (i) may be appropriately selected from among known methods depending on the binder component in the coloring composition. In the step of curing, at least the flowability is changed. For example, in the case where the coloring composition is a photosensitive coloring composition and the coloring layer is arranged in a pattern, exposure is performed through a mask of a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, etc. The coating film is cured in a pattern by polymerization reaction. As a light source used for exposure, ultraviolet rays, such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, an electron beam etc. are mentioned, for example. The exposure amount is appropriately adjusted depending on the light source to be used, the thickness of the coating film, and the like.

Next, development processing is performed using a developer, and the unexposed area is dissolved and removed to form a cured coating film of a desired pattern. As a developing solution, usually, a solution in which an alkali is dissolved in water or a water-soluble solvent is used. An appropriate amount of surfactant or the like may be added to the alkaline solution. Moreover, the developing method can employ | adopt a general method.
After the development processing, washing of the developing solution and drying of the cured coating film of the coloring composition are usually performed to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. There is no limitation in particular as heating conditions, According to the use of a coating film, it selects suitably.

(Step (iii))
The method for heating the cured coating is not particularly limited, but heating at a temperature above the temperature at which the fluorine-containing group is separated from the thermally-degradable fluorine-containing polymer contained in the colored composition of the present disclosure is preferred. .
Specifically, heating to 100 ° C. or higher is preferable, 150 ° C. or higher is more preferable, and heating to 200 ° C. or higher is even more preferable. The upper limit of the temperature may be appropriately adjusted in consideration of the heat resistance of a coloring material or the like, but is usually 350 ° C. or less, preferably 280 ° C. or less. The heating time may be appropriately adjusted according to the thickness of the cured coating film, etc., but is usually 5 minutes or more and 120 minutes or less, and preferably 10 minutes or more and 60 minutes or less.
In the step (iii), since the fluorine-containing group is separated from the (D) fluorine-containing polymer, the surface of the colored layer is not provided with the ultraviolet ray cleaning step conventionally performed before forming the covering layer. The hydrophilicity and lipophilicity are improved, and the wettability of the surface is excellent.
For example, when three colored layers are arranged in a pattern, a colored composition is prepared for each color, and these are respectively prepared as a first colored composition, a second colored composition, and a third colored composition. Then, by repeating the steps (i) to (iii) for each coloring composition, a cured coating film in the form of a pattern can be obtained. In the case of this example, between the step (iii) for the first coloring composition and the step (i) for the second coloring composition, and the steps (iii) and the third coloring for the second coloring composition It is preferred not to have a UV cleaning step between step (i) for the composition. By not having the ultraviolet ray cleaning step, it is possible to suppress the decrease in luminance due to the deterioration of the color material.
Although the case where the three colored layers are arranged in a pattern is taken as an example, the patterned colored layer is formed in the same manner in the case of two colored layers and in the case of four or more colored layers. be able to.

(Step (iv))
When providing a coating layer on a colored layer, it is preferable to perform a process (iv) following said process (iii). In particular, it is preferable not to have an ultraviolet ray cleaning step between the step (iii) and the step (iv). By not having the ultraviolet ray cleaning step, it is possible to suppress the decrease in luminance due to the deterioration of the color material.
The method for forming the covering layer may be appropriately selected from conventionally known methods according to the type of the covering layer. For example, in the case where the covering layer is the protective layer or the alignment film, the above-mentioned coloring composition using the composition for the protective layer or the composition for alignment film from the viewpoint of suppressing unevenness of the protective layer etc. It is preferable to form by the method similar to the process of forming the cured coating film of a thing.
When forming an alignment film as a coating layer, after forming a cured coating film by the said method, it can be set as an alignment film by providing orientation control force to an alignment film. The means for applying an alignment regulating force to the alignment film may be, for example, conventionally known one such as a rubbing method or a photoalignment method. In the present disclosure, the alignment control force means an interaction that aligns liquid crystal compounds on an alignment film in a specific direction.
When the covering layer is a transparent conductive layer such as the ITO film, it may be appropriately selected from conventionally known methods such as electron beam vapor deposition, physical vapor deposition, and sputter deposition.

[Liquid crystal display device]
A liquid crystal display device according to an embodiment of the present disclosure includes a color filter according to the above-described embodiment of the present disclosure, an opposing substrate, and a liquid crystal layer formed between the color filter and the opposing substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view showing an example of the liquid crystal display device of the present invention. As exemplified in FIG. 3, the liquid crystal display device 40 of this embodiment includes a color filter 10, an opposing substrate 20 having a TFT array substrate, etc., and a liquid crystal formed between the color filter 10 and the opposing substrate 20. And a layer 15. In FIG. 3, an alignment film 13a is formed on the side of the protective layer 5 formed on the colored layer 3 of the color filter 10, and an alignment film 13b is formed on the side of the opposing substrate 20. A liquid crystal is interposed between the two alignment films 13a and 13b. An example in which the layer 15 is formed is shown. Furthermore, in FIG. 3, the liquid crystal display device 40 includes a polarizing plate 25 a disposed outside the color filter 10, a polarizing plate 25 b disposed outside the opposing substrate 20, and the opposing substrate 20 of the liquid crystal display device 40. The example which has the back light 30 arrange | positioned outside the polarizing plate 25b arrange | positioned at the side is shown.
The liquid crystal display device of the present embodiment is not limited to the configuration shown in FIG. 3 and can be generally known as a liquid crystal display device using color filters.

The drive method of the liquid crystal display device of the present embodiment is not particularly limited, and a drive method generally used for a liquid crystal display device can be adopted. As such a driving method, for example, a TN method, an IPS method, an OCB method, an MVA method and the like can be mentioned. In the present embodiment, any of these methods can be suitably used.
In addition, the opposite substrate can be appropriately selected and used in accordance with the driving method and the like of the liquid crystal display device of the present disclosure.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy, and a mixture thereof can be used according to the driving method and the like of the liquid crystal display device of the present embodiment.

As a method of forming a liquid crystal layer, a method generally used as a method of 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 an opposite substrate, and the liquid crystal is heated to be an isotropic liquid, and the liquid crystal cell is isotropic liquid is made using the capillary effect. The liquid crystal layer can be formed by injecting in the state of and sealing with an adhesive. Thereafter, by gradually cooling the liquid crystal cell to room temperature, the enclosed liquid crystal can be aligned.
In the liquid crystal dropping method, for example, a sealing agent is applied to the peripheral edge of the color filter, the color filter is heated to a temperature at which the liquid crystal is isotropic, and the liquid crystal is dropped in the isotropic liquid state using a dispenser or the like. The liquid crystal layer can be formed by overlapping the color filter and the opposite substrate under reduced pressure and adhering them through a sealing agent. Thereafter, by gradually cooling the liquid crystal cell to room temperature, the enclosed liquid crystal can be aligned.

Moreover, as a backlight used for the liquid crystal display device of this embodiment, it can select suitably according to the use of a liquid crystal display device, and can use it. As the backlight, for example, a cold cathode fluorescent lamp (CCFL), a backlight unit using a white LED or a white organic EL as a light source can be provided in addition to a cold cathode fluorescent lamp (CCFL).
As the white LED, for example, a white LED which obtains white light by color mixing by combining red LED, green LED and blue LED, a white LED which obtains white light by color mixing combining blue LED, red LED and green phosphor, blue LED White LED to obtain white light by color mixing by combining red, green and red light emitting phosphors, White LED to obtain white light by mixing blue LED and YAG phosphor, ultraviolet light LED and red light emitting phosphor and green light emitting fluorescent light A white LED etc. which obtain white light by color mixing combining a body and a blue light emission fluorescent substance can be mentioned. A quantum dot may be used as the phosphor.

[Light emitting display]
A light emitting display device according to an embodiment of the present disclosure includes the color filter according to the embodiment of the present disclosure described above and a light emitter. Examples of the light emitting display device according to the present invention include an organic light emitting display device having an organic light emitting body as the light emitting body. A light-emitting body is not limited to an organic light-emitting body, An inorganic light-emitting body can also be used suitably.
Such a light emitting display device of the present embodiment will be described with reference to the drawings. FIG. 4 is a schematic view showing an example of the light emitting display device of the present embodiment. As illustrated in FIG. 4, the light emitting display device 100 of the present embodiment includes a color filter 10 and a light emitter 80. An inorganic oxide film 60 may be provided between the color filter 10 and the light emitter 80.

As a method of laminating the light emitter 80, for example, a method of sequentially forming 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 on the color filter Alternatively, the light-emitting body 80 formed on another substrate may be attached to the inorganic oxide film 60. 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 the other components in the light emitting body 80 may be appropriately known ones. The light emitting display device 100 manufactured in this manner is applicable to, for example, an organic EL display of a passive drive system and an organic EL display of an active drive system.
Note that the light emitting display device of the present embodiment is not limited to the light emitting display device having the configuration shown in FIG. 4 and may generally have a known configuration as a light emitting display device using a color filter. it can.

  Hereinafter, the present invention will be specifically described by way of examples. These descriptions do not limit the present invention.

Synthesis Example 1 Synthesis of Fluorine-Containing Monomer A
25 parts by mass of methacrylic acid and 101 parts by mass of 2- (perfluorohexyl) ethyl vinyl ether (product name: CHEMINOX FAVE-6, manufactured by Unimatec) are charged in a reactor equipped with a cooling pipe, an inlet for nitrogen, and a stirrer, and a nitrogen atmosphere The reaction was allowed to proceed at 60 ° C. for 9 hours. After cooling, an aqueous potassium carbonate solution was added to neutralize. The obtained reaction solution was washed with water, separated, the solvent was distilled off, and the unreacted component was removed by drying under reduced pressure to obtain a fluorine-containing monomer A.

Synthesis Example 2 Synthesis of Fluorine-Containing Monomer B
In a reactor equipped with a cooling pipe, an inlet for nitrogen, and a stirrer, 25 parts by mass of 2-hydroxyethyl methacrylate, 101 parts by mass of 2- (perfluorohexyl) ethyl vinyl ether (product name: CHEMINOX FAVE-6, manufactured by Unimatec), 2.0 parts by mass of trifluoroacetic acid and 200 parts by mass of tetrafudrofuran were charged, and reacted under nitrogen atmosphere at 60 ° C. for 9 hours. After cooling, an aqueous potassium carbonate solution was added to neutralize. The obtained reaction solution was washed with water, separated, the solvent was distilled off, and the unreacted component was removed by drying under reduced pressure to obtain a fluorine-containing monomer B.

Synthesis Example 3 Synthesis of Macromonomer A
80.0 parts by mass of PGMEA was charged in a reactor equipped with a cooling pipe, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and heated to a temperature of 90 ° C. while stirring under a nitrogen stream. A mixed solution of 100.0 parts by mass of isobutyl methacrylate, 4.0 parts by mass of mercaptoethanol, 30.0 parts by mass of PGMEA, and 1.0 parts by mass of AIBN was dropped over 1.5 hours, and reaction was further performed for 3 hours. Next, the nitrogen stream is stopped, and the reaction solution is cooled to 80 ° C., and 2-isocyanatoethyl methacrylate (product name: Karenz MOI, manufactured by Showa Denko) 8.74 parts by mass, dibutyltin dilaurate 0.125 A 50.0 mass% solution of macromonomer A was obtained by adding 3 mass parts, 0.125 mass parts of p-methoxyphenol, and 10.0 mass parts of PGMEA and stirring for 3 hours. Was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide added / polystyrene standard, mass average molecular weight (Mw) 3720, number average molecular weight (Mn) 1) The molecular weight distribution (Mw / Mn) was 2.14.

Synthesis Example 4 Synthesis of Fluorine-Containing Polymer A
80.0 parts by mass of PGMEA was charged in a reactor equipped with a cooling pipe, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 19.44 parts by mass of fluorine-containing monomer A of Synthesis Example 1, 40.56 parts by mass of polybutylene oxide macromonomer (product name: Blenmer 10PPB-500B, manufactured by NOF Corporation), 56.0 parts by mass of PGMEA, thermal polymerization initiator (product Name: V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) 1.2 parts by mass of a mixed solution is added dropwise over 1.5 hours, and after heating and stirring for 3 hours, V-65 0.12 parts by mass, PGMEA 4.0 parts by mass The liquid mixture of the above was added, and the mixture was further aged at the same temperature for 1 hour to obtain a fluorine-containing polymer A including the structure represented by the general formula (1-2). The solid content was adjusted to be 20% by mass by further adding PGMEA.

Synthesis Examples 5 to 7 Synthesis of Fluorine-Containing Polymers B to D
In Synthesis Example 4, a polybutylene oxide-based macromonomer is a polypropylene oxide-based macromonomer (product name: Blenmer PP-800, manufactured by NOF Corporation), a polycaprolactone-based macromonomer (product name: Plaxel FM5, manufactured by Daicel), a synthesis example A fluorine-containing polymer B including a structure represented by the general formula (1-2) in the same manner as in Synthesis Example 4 except that the macromonomer A of 3 (effective solid content: 40.56 parts by mass) was changed to each. We synthesized ~ D.

Synthesis Example 8 Synthesis of Fluorine-Containing Polymer E
In the same manner as in Synthesis Example 4 except that the fluorine-containing monomer A of Synthesis Example 1 is changed to the fluorine-containing monomer B of Synthesis Example 2 in Synthesis Example 4, the structure represented by the general formula (1-1) is obtained. The fluorine-containing polymer E containing was synthesize | combined.

Comparative Synthesis Example 1: Synthesis of Fluorine-Containing Polymer F
A fluorine is prepared in the same manner as in Synthesis Example 4 except that, in Synthesis Example 4, the fluorine-containing monomer A of Synthesis Example 1 is changed to 2- (perfluorohexyl) ethyl methacrylate (product name: CHEMINOX FAMAC-6, manufactured by Unimatec). Containing polymer F was synthesized.

Comparative Synthesis Examples 2 to 4 Synthesis of Fluorine-Containing Polymers GI
In Comparative Synthesis Example 1, a polybutylene oxide macromonomer is a polypropylene oxide macromonomer (product name: Brenmer PP-800, manufactured by NOF Corporation), a polycaprolactone macromonomer (product name: Plaxel FM5, manufactured by Daicel), synthesis Fluorine-containing polymers G to I were synthesized in the same manner as in Comparative Synthesis Example 1 except that the macromonomer A (effective solid content: 40.56 parts by mass) of Example 3 was changed.

  For the fluorine-containing polymers A to H, mass average molecular weight (Mw), number average molecular weight (Mn), and N-methyl pyrrolidone, 0.01 mol / L lithium bromide addition / polystyrene standard conditions by GPC, respectively, and The molecular weight distribution (Mw / Mn) was determined. The results are shown in Table 1.

The fluorine-containing polymers A to E obtained in Synthesis Examples 4 to 8 have a fluorine-containing group in a temperature range of 100 ° C. or more and 250 ° C. or less by thermal weight loss (TG) measurement and gas chromatography mass spectrometry (GCMS) measurement. It was confirmed that the polymer was a thermally decomposable fluorine-containing polymer which was released. Moreover, it was confirmed that the fluorine-containing group does not separate | leave in the temperature range of 100 degreeC or more and 250 degrees C or less of fluorine-containing polymers F-I obtained by the comparative synthesis examples 1-4.
Furthermore, as a result of GCMS measurement at 230 ° C. for 30 minutes, a thermal decomposition product derived from 2- (perfluorohexyl) ethyl vinyl ether is detected from the fluorine-containing polymers A to E obtained in Synthesis Examples 4 to 8 However, the thermal decomposition product of the fluorine-containing group was not detected from the fluorine-containing polymers F to I in Comparative Synthesis Examples 1 to 4.
In addition, DTG-60A made from Shimadzu was used for the measurement of thermal-gravity reduction, the measurement temperature range was 10 degreeC / min and the temperature increase rate was 10 degreeC / min from room temperature. GCMS measurement was performed under the following conditions.

<Measurement conditions>
GCMS device: manufactured by Agilent Technologies
HP-5973N / 6890N
Thermal decomposition method: Continuous thermal decomposition method (PY-2020 iD type)
Heat extraction temperature: 230 ° C (30 min)
Inlet temperature: 320 ° C
Column: 5% phenyl-95% dimethyl siloxane (UA-5) slightly polar diameter: 0.25 μm length: 30 m
Column temperature: 50 ° C. × 5 min (holding) −10 ° C./min (heating) −320 ° C. × 3 min (holding)
Ionization method: Electron impact ionization method (EI method)
Detector: Quadruple detector

Synthesis Example 9 Synthesis of Color Material A
(1) Synthesis of Intermediate A-1 15.9 g (yield: 70%) of the following Intermediate A-1 with reference to the method for producing Intermediate 3 and Intermediate 4 described in WO 2012/144521 )Obtained.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), Divalent Elemental Analysis: CHN found (78.13%, 7.48%, 7.78%); theoretical value (78.06%) , 7.75%, 7.69%)

(2) Synthesis of Coloring Material A 5.00 g (4.58 mmol) of the intermediate A-1 was added to 300 ml of water and dissolved at 90 ° C. to obtain an intermediate A solution. Next, 10.44 g (3.05 mmol) of phosphotungstic acid n hydrate H ₃ [PW ₁₂ O ₄₀ ] n H ₂ O (n = 30) (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) is added to 100 ml of water, and 90 ° C. The solution was stirred to prepare an aqueous solution of phosphotungstic acid. The phosphotungstic acid aqueous solution prepared above was mixed with the intermediate A-1 solution at 90 ° C., and the formed precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g of a blue coloring material (coloring material A) of a triarylmethane basic dye represented by the following chemical formula A.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 510 (+), Divalent Elemental Analysis: CHN found (41.55%, 5.34%, 4.32%); theoretical value (41.66%) , 5.17%, 4.11%)

Synthesis Example 10 Synthesis of Color Material B
(1) Synthesis of Intermediate B-1 15.2 g (60 mmol) of 1-iodonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.), 7.15 g of 4,4′-methylenebis (2-methylcyclohexylamine) (manufactured by Tokyo Chemical Industry Co., Ltd.) 30 mmol), sodium tert-butoxide 8.07 g (84 mmol), Aldrich 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl 0.09 g (0.2 mmol), palladium acetate (Wako Pure Chemical Industries) 0 .021 g (0.1 mmol) was dispersed in 30 mL of xylene and reacted at 130 to 135 ° C. for 48 hours. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with water. Subsequently, 13.84 g (yield 94%) of the following intermediate B-1 were obtained by drying with magnesium sulfate and concentration.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 491 (M + H), 2879 (MH2-)
Elemental analysis value: CHN actual measurement value (85.72%, 8.53%, 5.75%); theoretical value (85.66%, 8.63%, 5.71%)

(2) Synthesis of Intermediate B-2 15.0 g (59.7 mmol) of Wako Pure Chemical Industries 4,4′-dichlorobenzophenone (Wako Pure Chemical Industries, Ltd.), N-ethyl-o-toluidine (Wako Pure Chemical Industries, Ltd.) 16 .3 g (121 mmol), sodium-tert-butoxide 16.1 g (168 mmol), 2-dicyclohexylphosphino-2 ', 4', 6 ', triisopropylbiphenyl (from Johnson Matthey) 2.86 g (6.0 mmol) The reaction solution was dispersed in 673 mg (3.0 mmol) of palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and 130 mL of xylene and reacted at 100 to 105 ° C. for 20 hours. After completion of the reaction, the reaction solution was cooled to room temperature and extracted by adding 200 ml of toluene and 200 ml of water. The toluene solution was dried over magnesium sulfate and concentrated under reduced pressure. The residue was diluted with toluene and purified by silica gel column chromatography to obtain 11.8 g (yield 44%) of the following intermediate B-2.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 449 (M + H),
Elemental analysis value: CHN actual measurement value (82.90%, 7.33%, 6.22%); theoretical value (82.81%, 7.40%, 6.23%)

(3) Synthesis of Intermediate B-3 2.98 g (6.08 mmol) of Intermediate B-1 obtained above, 6.00 g (13.4 mmol) of Intermediate B-2 and 10 mL of chlorobenzene were mixed to obtain 45 Stir at -50 ° C. 2.06 g (13.4 mmol) of phosphorus oxychloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was stirred at 45 to 50 ° C. for 20 hours. After completion of the reaction, 100 ml of chloroform and 100 ml of water were added and dissolved, and the chloroform layer was separated. The chloroform layer was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was diluted with chloroform and purified by silica gel column chromatography to obtain 7.54 g of the following intermediate B-3 (yield 87%).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 677 (+), Divalent Elemental Analysis: CHN found (81.81%, 7.31%, 5.85%); theoretical value (81.77%) , 7.36%, 5.90%)

(4) Synthesis of Coloring Material B Phosphorus tungstic acid n-hydrate was prepared by dissolving 1.7 g (1.19 mmol) of the intermediate B-3 in 170 mL of methanol and heating and dissolving it in a mixture of 40 mL of methanol and 40 mL of water. 2.59 g (0.76 mmol) of H ₃ [PW ₁₂ O ₄₀ ] .n H ₂ O (n = 30) (manufactured by Nippon Inorganic Chemical Industry) were added, and the mixture was stirred for 1 hour. The precipitate was collected by filtration and washed with water. The obtained precipitate was dried under reduced pressure to obtain 3.4 g (yield: 95%) of a blue coloring material (coloring material B) represented by the following chemical formula B.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (MALDI) (m / z): 1355 (M +), 2879 (MH2-)
Elemental analysis value: CHN actual measurement value (35.55%, 3.24%, 2.61%); theoretical value (35.61%, 3.20%, 2.57%)

Synthesis Example 11 Synthesis of Color Material C
5.0 g of Acid Red 289 was added to 500 ml of water and dissolved at 80 ° C. to prepare a dye solution. 3.85 g of polyaluminum chloride ("Takibine # 1500" manufactured by Taki Chemical Co., Al ₂ (OH) ₅ Cl, basicity 83.5% by mass, 23.5% by mass as alumina) in 200 ml of water The solution was dissolved to prepare an aqueous solution of polyaluminum chloride. The prepared polyaluminum chloride aqueous solution was added dropwise to the dye solution at 80 ° C. for 15 minutes, and 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 6.30 g (96.2% yield) of a purple rhodamine acid dye salt-forming coloring material (coloring material C).

Synthesis Example 12 Synthesis of Color Material D
5.0 g of Acid Red 289 was added to 500 ml of water and dissolved at 80 ° C. to prepare a dye solution. ARCARD 2 HP flakes (Lion Akzo, dimethyl distearyl ammonium chloride, 95.5% effective solids), 4.99 g, was dissolved in 85 g of isopropyl alcohol to prepare a dimethyl distearyl ammonium chloride solution. The dye solution was cooled to 5 ° C. with an ice bath, and the prepared dimethyl distearyl ammonium chloride solution was added dropwise to the dye solution over 25 minutes at 5 ° C., and further stirred at 5 ° C. for 1 hour. The formed precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 9.07 g (yield 97%) of a purple rhodamine acid dye salt-forming coloring material (coloring material D).

Synthesis Example 13 Synthesis of Binder Resin A
In a reactor equipped with a cooling pipe, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 120 parts by mass of PGMEA is charged as a solvent, heated to 90 ° C. under a nitrogen atmosphere, and 32 parts by mass of methyl methacrylate A mixture containing 10 parts by mass, 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 over 1.5 hours Dripped into the
Thereafter, the reaction is continued while maintaining the synthesis temperature, and as a polymerization inhibitor two hours after the completion of dropping,
0.05 parts by mass of p-methoxyphenol was added.
Next, 22 parts by mass of glycidyl methacrylate is added while blowing in air, and the temperature is raised to 110 ° C. 0.2 parts by mass of triethylamine is then added to cause addition reaction at 110 ° C. for 15 hours. The solid content was 45% by mass).
The obtained binder resin A had a weight average molecular weight (Mw) 8850, a number average molecular weight (Mn) 4200, a molecular weight distribution (Mw / Mn) of 2.11 and an acid value of 78 mg KOH / g.

Production Example 1: Preparation of Salt-type Block Polymer Dispersant A Solution
60.74 parts by mass of PGMEA and a block copolymer containing tertiary amino groups (trade name: BYK-LPN6919, manufactured by BYK-Chemie) in a reactor (amine value 120 mg KOH / g, solid content 60% by weight) 35.64 parts by mass ( 21.38 parts by mass of effective solids) are dissolved, 3.62 parts by mass of PPA (0.5 molar equivalent relative to the tertiary amino group of the block copolymer) is added, and the mixture is stirred at 40 ° C. for 30 minutes Thus, a salt type block polymer dispersant A solution (solid content 25%) was prepared.

(Production Example 2: Production of Colorant Dispersion A)
13.00 parts by mass of a coloring material A of Synthesis Example 9 as a coloring material, 18.20 parts by mass of a dispersant A solution of Production Example 1 (solid content: 4.55 parts by mass), Binder resin A of Synthesis Example 13 Parts by mass (solid content 5.85 parts by mass) and 55.80 parts by mass of PGMEA are mixed and pre-dispersed with a paint shaker (Asada Iron Works Co., Ltd.) for 1 hour with 2 mm zirconia beads and further with 0.1 mm zirconia beads for main dispersion The mixture was dispersed for 4 hours to obtain a colorant dispersion A.

Production Example 3 Production of Colorant Dispersion B
A colorant dispersion liquid B was obtained in the same manner as in Production Example 2 except that the colorant was changed to 13.00 parts by mass of the colorant B in Synthesis Example 10.

Production Example 4 Production of Colorant Dispersion C
Color material dispersion liquid C in the same manner as in Production Example 2 except that the colorant is changed to 12.22 parts by mass of the colorant A of Synthesis Example 9 and 0.78 parts by mass of the colorant C of Synthesis Example 11 I got

(Production Example 5: Production of Colorant Dispersion D)
A color material dispersion liquid in the same manner as in Production Example 2 except that the color material is changed to 12.22 parts by mass of the blue color material A of Synthesis Example 9 and 0.78 parts by mass of the color material D of Synthesis Example 12 I got D.

Production Example 6: Production of Colorant Dispersion E
A color material dispersion E was obtained in the same manner as in Example 2 except that the color material was changed to 13.0 parts by mass of a phthalocyanine-based pigment (Pigment Blue 15: 6).

Production Example 7 Preparation of Binder Composition A
PGMEA 44.36 parts by mass, binder resin A (solid content 45% by mass) of Synthesis Example 13 (28.44 parts by mass), 5- to 6-functional acrylate monomer (trade name: Alonix M402, manufactured by Toagosei Co., Ltd.) 19.20 parts by mass, 2 -Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF) 6.00 parts by mass, 2,4 diethylthioxanthone (trade name: Kayacure DETX) Binder composition A (solid content: 40% by mass) was prepared by mixing 2.00 parts by mass of -S (manufactured by Nippon Kayaku Co., Ltd.).

Preparation Example 8 Preparation of Coating Layer Composition
(1) Synthesis of polyesteramide acid 143.5 parts by mass of 3,3 ', 4,4'-diphenylethertetracarboxylic acid dianhydride and 25.0 parts of 1,4-butanediol in a four-necked flask equipped with a stirrer Parts, 20.0 parts by mass of benzyl alcohol, 23.0 parts by mass of 3,3'-diaminodiphenyl sulfone, 493.0 parts by mass of methyl 3-methoxypropionate as a solvent are charged, and heated at 130 ° C. for 3 hours in a nitrogen atmosphere The polymerization was carried out to obtain a 30% by mass solution of polyesteramic acid.

(2) Preparation of composition for covering layer 16.0 parts by mass of a 30% by mass solution of the above polyester amic acid, 9.5 parts by mass of epoxy resin (trade name: EHPE 3150, manufactured by Daicel), trimellitic anhydride 0.9 0.3 parts by mass of 3-glycidoxypropyl trimethoxysilane (trade name: KBM 403, manufactured by Shin-Etsu Chemical Co., Ltd.), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] (trade name: Irganox 1010, manufactured by BASF) 0.2 parts by mass, 108.8 parts by mass of methyl 3-methoxypropionate, 0.05 part by mass of a fluorinated surfactant (trade name: Megafac F 447, manufactured by DIC) The composition for coating layers (20 mass% of solid content) was prepared by mixing.

Example 1
(1) Preparation of photosensitive coloring composition A 33.57 parts by mass of the color material dispersion A obtained in Production Example 2, 25.23 parts by mass of the binder composition A obtained in Production Example 7, 40.65 parts of PGMEA Part, 0.25 parts by mass (0.05 parts by mass of effective solid content) of the fluorine-containing polymer A of Synthesis Example 4 as a leveling agent is added and mixed, pressure filtration is performed, and a photosensitive coloring composition A of Example 1 is obtained. I got

(2) Preparation of Colored Cured Film The photosensitive colored composition A obtained in the above (1) was applied to a glass substrate having a thickness of 0.7 mm (manufactured by Nippon Electric Glass, "OA-10G") using a spin coater. Applied. Then, it heat-dried on the 80 degreeC hotplate for 3 minutes. A blue colored cured film was obtained by irradiation with ultraviolet light of 40 mJ / cm ² using an ultrahigh pressure mercury lamp. The substrate on which the cured film was formed was post-baked for 30 minutes in a clean oven at 230 ° C. The chromaticity after curing was made to be y = 0.082.

(3) Formation of Coating Layer The composition for a coating layer prepared in Production Example 8 was applied to the colored cured film obtained in the above (2) using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate, and also post-baked for 30 minutes in a 230 degreeC clean oven.

<Leveling evaluation>
About the colored cured film obtained by said (2), the presence or absence of the nonuniformity of the film surface was observed with the microscope. The results are shown in Table 2.
○: no unevenness ×: unevenness

<Recoatability evaluation>
The presence or absence of repelling at the time of spin-coating the composition for coating layers by said (3) was confirmed visually. The results are shown in Table 2.
○: no repelling ×: no repelling

<Optical performance evaluation>
The chromaticity (x, y) and the luminance (Y) of the finally obtained colored film were measured using a "microspectroscopic light measuring device OSP-SP200" manufactured by Olympus. The chromaticity (x, y) and luminance (Y) of the colored film are shown in Table 2.

(Examples 2-5, comparative examples 1-4)
In Example 1 (1), in place of the fluorine-containing polymer A of Synthesis Example 4 as a leveling agent, the fluorine-containing polymers B to E of Synthesis Examples 5 to 8 and the fluorine-containing polymers F to F of Comparative Synthesis Examples 1 to 4 The photosensitive coloring compositions of Examples 2 to 5 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1 (1) except that each of them was changed to I, and the performance evaluation was carried out in the same manner as Example 1. . The results are shown in Table 2.

(Comparative example 5)
A photosensitive coloring composition of Comparative Example 5 was prepared in the same manner as in Example 1 except that no leveling agent was added in Example 1 (1), and the performance was evaluated in the same manner as in Example 1. . The results are shown in Table 2.

(Comparative Examples 6 to 9)
Example 1 except that the photosensitive coloring compositions of Comparative Examples 1 to 4 were subjected to ultraviolet irradiation for 5 minutes using a low pressure mercury lamp between the steps (2) and (3) of Example 1. Performance evaluation was performed in the same manner as in. The results are shown in Table 2.

(Examples 6-8, comparative examples 10-14)
The types of coloring material and fluorine-containing polymer are changed according to Table 2 and Table 3, respectively, and photosensitive colored resin compositions of Examples 6 to 8 and Comparative Examples 10 to 14 are prepared, and ultraviolet irradiation is performed according to Table 2 and Table 3. The performance evaluation was performed by changing the presence or absence of The results are shown in Tables 3 and 4. The column of color materials in Table 4 indicates the combination of color materials and the content ratio (mass ratio) of the color materials.

[Result Summary]
The colored layer of Comparative Example 5 containing no fluorine-containing polymer had poor leveling properties and poor smoothness.
The colored layer of Comparative Examples 1 to 4 containing a fluorine-containing polymer which is not a thermal decomposition-type fluorine-containing polymer repelled the composition for a coating layer when the ultraviolet ray cleaning step was not performed, and the recoatability was poor. . On the other hand, although recoating property was improved by performing an ultraviolet-ray washing | cleaning process (comparative examples 6-9), the brightness | luminance of the colored layer was falling compared with Examples 1-5.
It formed using the coloring composition of Examples 1-5 which contains the salt-forming coloring material of a dye, and the thermal decomposition type fluorine-containing polymer from which a fluorine-containing group detach | desorbs in the temperature range of 100 degreeC-250 degreeC. The colored layer was found to be excellent in smoothness, excellent in recoatability without providing an ultraviolet ray cleaning step, and to be a high-brightness colored layer.
As shown by the comparison between Example 6 and Comparative Example 10, and the comparison between Examples 7 to 8 and Comparative Examples 11 to 14, according to the resin composition of the present disclosure, high brightness and high smoothness can be obtained. It became clear that it becomes possible to form a colored layer which has a property and is easy to form a covering layer on the surface.

DESCRIPTION OF SYMBOLS 1 transparent substrate 2 light-shielding part 3 coloring layer 4 coating layer 5 protective layer 10 color filter 13a, 13b alignment film 15 liquid crystal layer 20 opposing substrate 25a, 25b polarizing plate 30 back light 40 liquid crystal display 60 inorganic oxide film 71 transparent anode 72 positive electrode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Light emitter 100 Light emitting display

Claims (11)

(A) a colorant, (B) a dispersant, (C) a binder component, (D) a fluorine-containing polymer, and (E) a solvent,
The (A) colorant contains a dye-forming salt colorant,
The coloring composition in which the said (D) fluorine-containing polymer contains the thermal decomposition type fluorine-containing polymer from which a fluorine-containing group detach | leaves in a temperature range of 100 degreeC or more and 250 degrees C or less. The (D) fluorine-containing polymer is a polymer containing, in a side chain, one or more types of structures selected from the following general formula (1-1) and the following general formula (1-2). The coloring composition as described in.

(In the general formula (1-1) and the general formula (1-2), L ¹ represents an oxygen atom or a sulfur atom, and R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent R _f represents a fluorine atom-containing alkyl group or a fluorine atom-containing polyalkylene ether group, and R ¹ and R each represent a hydrocarbon group having 1 to 18 carbon atoms which may have one or more carbon atoms. _f may combine to form a ring structure) (A) a colorant, (B) a dispersant, (C) a binder component, (D) a fluorine-containing polymer, and (E) a solvent,
The (A) colorant contains a dye-forming salt colorant,
A coloring composition in which the (D) fluorine-containing polymer is a polymer including at least one structure selected from the following general formula (1-1) and the following general formula (1-2) in a side chain .

(In the general formula (1-1) and the general formula (1-2), L ¹ represents an oxygen atom or a sulfur atom, and R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent R _f represents a fluorine atom-containing alkyl group or a fluorine atom-containing polyalkylene ether group, and R ¹ and R each represent a hydrocarbon group having 1 to 18 carbon atoms which may have one or more carbon atoms. _f may combine to form a ring structure)   The coloring composition of Claim 1 or 3 in which the said (A) coloring material contains 1 or more types selected from a triarylmethane type coloring material and a xanthene type coloring material. The coloring composition of Claim 1 or 3 in which the said (A) coloring material contains the coloring material represented with the following general formula (I).

(In general formula (I), A is an a-valent organic group in which a carbon atom directly bonded to N does not have a π bond, and the organic group is a saturated aliphatic carbon group at the end directly linked to N Aliphatic hydrocarbon group which has a hydrogen group and may contain O, S, N in its carbon chain, or has an aliphatic hydrocarbon group at the end directly bonded to N, and has O in its carbon chain , S and N represent an aromatic group which may be contained,
R ^{i, R ii,} R ^{iii, R iv,} and ^{R v} each independently represent a hydrogen atom, which may have a an optionally substituted alkyl group or a substituted aryl ^{group, R ii} and R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure.
R ^vi and R ^vii each independently represent an alkyl group which may have a substituent or an alkoxy group which may have a substituent,
Ar ⁱ represents a divalent aromatic group which may have a substituent,
B ^c- represents a c-valent anion,
a and c are integers of 2 or more, b and d are integers of 1 or more, e is 0 or 1, f and g are integers of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less ,
Plural R ^{i to} R ^vii , Ar ⁱ , e, f and g may be the same or different. )   A color filter having a colored layer on a transparent substrate, wherein at least one of the colored layers is a cured product of the colored composition according to claim 1 or 3.   The color filter according to claim 6, further comprising a covering layer on the colored layer. A method for producing a color filter having a colored layer on a transparent substrate, comprising:
Forming a coating film of the colored composition according to any one of claims 1 to 5 on a transparent substrate;
Curing the coating (ii);
And a step (iii) of heating the cured coating film. After the step (iii), the method further comprises the step (iv) of forming a coating layer on the colored layer,
The manufacturing method of the color filter of Claim 8 which does not have an ultraviolet-ray washing | cleaning process between the said process (iii) and the said process (iv).   A liquid crystal display device comprising the color filter according to claim 6, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.   A light emitting display comprising the color filter according to claim 6 and an organic light emitter.

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