TWI742096B - Color composition, color filter, method for producing color filter, liquid crystal display device and light-emitting display device - Google Patents

Abstract

The present invention provides a coloring composition, which contains (A) a colorant, (B) a dispersant, (C) a binder component, (D) a fluoropolymer, and (E) a solvent. The (A) colorant contains a dye The above-mentioned (D) fluorine-containing polymer contains fluorine-containing fluorine-containing pyrolysis type fluorine-containing polymer in a temperature range above 100°C and below 250°C.

Description

Coloring composition, color filter and manufacturing method thereof, liquid crystal display device and light-emitting display device

The embodiment of the present invention relates to a coloring composition, a color filter and a manufacturing method thereof, 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 has increased. The penetration rate of household LCD TVs has also increased, and the market for LCD monitors is expanding. In addition, recently, light-emitting display devices such as organic EL (Electroluminescence) displays, which are self-luminous and have high visibility, are also attracting attention as next-generation image display devices. Among the performance of these image display devices, there is a strong desire for further enhancement of image quality, such as improvement of contrast and color reproducibility, and reduction of power consumption.

Color filters are used in these display devices. For example, in the formation of a color image of a liquid crystal display device, the light passing through the color filter is directly colored into the color of each pixel constituting the color filter, and the light of these colors is synthesized to form a color image. In addition, in the light-emitting display device, when a color filter is used for a white light-emitting element, a color image is formed in the same manner as a liquid crystal display device.

Under such circumstances, color filters are also expected to increase in brightness and contrast. Or the improvement of color reproducibility.

Here, the color filter usually has a transparent substrate, a coloring layer containing coloring patterns of the three primary colors of red, green, and blue formed on the transparent substrate, and a light-shielding portion formed on the transparent substrate in a manner of dividing each coloring pattern.

As a method for achieving high brightness, the use of a coloring resin composition containing a dye as a composition for forming a colored layer has been studied. Compared with pigments, dyes usually have a higher transmittance and can produce high-brightness color filters. However, dyes tend to fade due to ultraviolet radiation, etc., and the brightness of the colored layer tends to decrease.

On the other hand, the coloring layer of the color filter requires high smoothness from the viewpoint of reduction of color unevenness. As a method for improving smoothness, it is known to add a leveling agent etc. to a colored resin composition. However, there are situations where the leveling agent is concentrated on the surface of the colored layer, resulting in a decrease in the wettability of the surface. Therefore, when a protective layer or the like is provided on the colored layer, there is a problem that the composition for the resin layer is easily repelled by the surface of the colored layer, and unevenness of the coating film is likely to occur. As a method for solving this problem, a method for improving the wettability of the colored layer surface by providing an ultraviolet cleaning step in which ultraviolet rays are irradiated on the surface of the colored layer is known.

In addition, for example, in Patent Document 1, it is possible to provide high smoothness to each pixel of a color filter or a protective film of the pixel, and a coating agent or the like can be applied to the pixel or the protective film well. The resin of the composition discloses a fluorine-containing thermally decomposable resin with a specific structure.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2016-17172

The purpose of the embodiments of the present invention is to provide a coloring composition that can form a coloring layer with high brightness and high smoothness, easy to form a coating layer on the surface, a color filter with a high brightness and smooth coloring layer, and The manufacturing method thereof includes a liquid crystal display device and a light-emitting display device having the color filter.

An embodiment of the present invention provides a coloring composition, which contains (A) a colorant, (B) a dispersant, (C) a binder component, (D) a fluoropolymer, and (E) a solvent. (A) ) The colorant contains a salt-forming colorant of a dye, and the above-mentioned (D) fluoropolymer contains a thermally decomposable fluoropolymer that decomposes based on a temperature range of 100°C or more and 250°C or less.

An embodiment of the present invention provides a coloring composition, which contains (A) a colorant, (B) a dispersant, (C) a binder component, (D) a fluoropolymer, and (E) a solvent. (A) ) The colorant contains a salt-forming colorant of dye, and the above-mentioned (D) fluoropolymer contains at least one selected from the following general formula (1-1) and the following general formula (1-2) in the side chain The structure of the polymer.

(In general formula (1-1) and general formula (1-2), L ¹ represents an oxygen atom or a sulfur atom, R ¹ , R ² and R ³ each independently represent a hydrogen atom, and the number of carbon atoms that may have a substituent is 1 or more and 18 or less hydrocarbon groups, R _f represents an alkyl group having a fluorine atom or a polyalkylene ether group having a fluorine atom; R ¹ and R _f may be bonded to form a ring structure).

An embodiment of the present invention provides a coloring composition, wherein the (A) color material contains one or more selected from the group consisting of triarylmethane color materials and dibenzopyran color materials.

An embodiment of the present invention provides a coloring composition, wherein the above-mentioned (A) colorant contains a colorant represented by the following general formula (I).

(In the general formula (I), A is an organic group with a valence of a carbon atom directly bonded to N without a π bond. The organic group means that at least the terminal directly bonded to N has a saturated aliphatic hydrocarbon group and is in the carbon chain It may contain O, S, N aliphatic hydrocarbon groups, or the end directly bonded to N has aliphatic hydrocarbon groups and the carbon chain may contain O, S, N aromatic groups, R ⁱ , R ⁱⁱ , R ⁱⁱⁱ , R ^iv and R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may be bonded to form a ring structure; R ^vi and R ^vii each Independently represent an optionally substituted alkyl group or an optionally substituted alkoxy group, Ar ⁱ represents an optionally substituted divalent aromatic group, B ^c- represents a c-valent anion, and a and c represent 2 or more Integer, b and d represent an integer of 1 or more, e represents 0 or 1, f and g represent an integer of 0 or more and 4 or less, f+e and g+e are 0 or more and 4 or less, and there are plural R ⁱ ~ R ^vii , Ar ⁱ , e, f and g may be the same or different).

An embodiment of the present invention provides 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 representing the embodiment of the present invention.

An embodiment of the present invention provides a color filter, wherein a coating layer is further provided on the colored layer.

An embodiment of the present invention provides a method for manufacturing a color filter, which is a method for manufacturing a color filter with a colored layer on a transparent substrate; and has: step (i), which is formed on the transparent substrate The above-mentioned coating film of the coloring composition of one embodiment of the present invention; step (ii), which is to harden the above-mentioned coating film; and step (iii), which is to heat the hardened coating film.

One embodiment of the present invention provides a method for manufacturing a color filter, which further includes a step (iv) of forming a coating layer on the colored layer after the above step (iii), and the above step (iii) is the same as the above step (iv) There is no ultraviolet cleaning step in between.

An embodiment of the present invention provides a liquid crystal display device having the color filter according to an embodiment of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate .

An embodiment of the present invention provides a light-emitting display device having the above-mentioned present invention One embodiment is a color filter and an organic light-emitting body.

According to the embodiment of the present invention, it is possible to provide a coloring composition that can form a coloring layer with high brightness, high smoothness, and easy to form a coating layer on the surface, a color filter with a high brightness and smooth coloring layer, and The manufacturing method thereof includes a liquid crystal display device and a light-emitting display device having the color filter.

1: Transparent substrate

2: Shading part

3: Coloring layer

4: Coating layer

5: protective layer

10: Color filter

13a, 13b: Alignment film

15: Liquid crystal layer

20: Opposite substrate

25a, 25b: Polarizing plate

30: Backlight

40: Liquid crystal display device

60: Inorganic oxide film

71: Transparent anode

72: hole injection layer

73: hole transport layer

74: luminescent layer

75: electron injection layer

76: cathode

80: luminous body

100: Light-emitting display device

Fig. 1 is a schematic cross-sectional view showing an embodiment of a color filter.

Fig. 2 is a schematic cross-sectional view showing an embodiment of a color filter.

Fig. 3 is a schematic cross-sectional view showing an embodiment of a liquid crystal display device.

4 is a schematic cross-sectional view showing an embodiment of an organic light-emitting display device.

Hereinafter, embodiments or examples of the present invention will be described with reference to the drawings and the like. However, the present invention can be implemented in many different aspects, and is not limited to the description of the following embodiments or examples. In addition, as a drawing, in order to make the description clearer, there are cases where the width, thickness, shape, etc. of each part are shown schematically in comparison with the actual state, but it is only an example and does not limit the interpretation of the present invention. In addition, in this specification and the drawings, the same reference numerals are sometimes given to the same elements as the above-mentioned elements in the drawings that have appeared, and detailed descriptions are omitted as appropriate. In addition, for the convenience of explanation, there are cases where the above or below sentences are used for explanation, but the up and down direction can be reversed.

In this specification, when a certain component or a certain area is "upper (or below)" of other components or other areas, etc., as long as there is no special limitation, it is not only in those other structures. The situation directly above (or directly below) also includes other components The above (or below) situation, that is, the situation where other components may be contained in the middle above (or below) of other components.

Furthermore, in the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and further radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less.

In the present invention, the so-called (meth)acrylic acid refers to both acrylic acid and methacrylic acid, and the so-called (meth)acrylate refers to both acrylic acid ester and methacrylic acid ester.

1. Coloring composition

The coloring composition of the present invention contains (A) colorant, (B) dispersant, (C) binder component, (D) fluoropolymer and (E) solvent, and the above-mentioned (A) colorant contains the salt of dye The colorant, the above-mentioned (D) fluoropolymer contains a thermally decomposable fluoropolymer from which fluorine is desorbed in a temperature range of 100°C or more and 250°C or less.

The coloring composition of the present invention can form a high brightness, high smoothness, and easy to form a coloring layer of a coating layer on the surface by combining a salt-forming colorant of a dye and a specific thermally decomposable fluoropolymer.

Since the past, as the coloring layer of color filters, high smoothness has been required from the viewpoint of reduction of color unevenness. As a method for improving smoothness, a method of adding a fluorine-based leveling agent to the coloring composition has been implemented conventionally. However, there are situations where the leveling agent is concentrated on the surface of the colored layer, resulting in a decrease in the wettability of the surface. Therefore, when 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 unevenness of the coating film is likely to occur. As a solution to this problem, an ultraviolet cleaning step of irradiating ultraviolet rays on the surface of the colored layer is implemented to improve the surface of the colored layer. Methods of wettability, etc. Previously, as the coloring material in the coloring composition, a pigment with excellent light resistance was generally used. Therefore, by the above method, a colored layer with good smoothness and a coating layer without uneven coating can be formed. On the other hand, from the viewpoint of further enhancing the brightness of the color filter, the inventors of the present invention have begun to study the use of a dye-containing coloring composition to form a coloring layer. It is known that when the above-mentioned ultraviolet cleaning step is applied to the colored layer containing dye, the brightness of the colored layer may decrease instead. The inventors of the present invention conducted intensive research based on this insight and found that by using a combination of dye-based salt-forming pigments and specific thermally decomposable fluoropolymers, high brightness, high smoothness, and ease of use can be formed. The colored layer of the coating film is formed on the surface.

The coloring composition of the present invention contains the salt-forming color material of the dye as the (A) color material. High brightness can be achieved by using dyes, and heat resistance can also be improved by chlorinating the dyes.

In addition, the coloring composition of the present invention contains a specific thermally decomposable fluoropolymer as the (D) fluoropolymer, so the coloring layer formed using the coloring composition has high smoothness. Furthermore, when a protective layer or the like is further formed on the colored layer, by heating the colored layer at 100°C or higher and 250°C or lower, the (D) fluoropolymer contained on the surface of the colored layer is concentrated The fluorine group is removed and the wettability of the surface is improved, so the unevenness of the coating film such as the protective layer can be suppressed. Therefore, there is no need for the previous ultraviolet cleaning step to improve the wettability of the surface. Therefore, even if it is a colored layer containing dyes that are easily faded by ultraviolet rays, the decrease in brightness can be suppressed, and a high-brightness colored layer can be obtained.

In this way, the coloring composition of the present invention can form a high brightness, high smoothness, and easy to form a coloring layer of a coating layer on the surface by using a salt-forming color material of a dye and a specific thermally decomposable fluoropolymer.

The coloring composition of the embodiment of the present invention contains at least (A) colorant, (B) dispersant, (C) binder component, (D) fluoropolymer and (E) solvent, and may contain others as needed Element.

Hereinafter, for this coloring composition, the (D) fluorine-containing polymer will be described first, and then each component will be described in order.

(D) Fluoropolymer

In the embodiment of the present invention, the (D) fluoropolymer contains a thermally decomposable fluoropolymer in which fluorine is desorbed in a temperature range of 100°C or more and 250°C or less. The thermally decomposable fluoropolymer has a fluorine-containing group before heating, so the coating film of the coloring composition can be smoothed. By heating the coating film after hardening, the fluorine-containing group is released, and the wettability of the coloring layer surface Improve, easy to form a coating layer.

In the present invention, the thermally decomposable fluoropolymer is not particularly limited as long as at least a part of the fluorine-containing polymer is desorbed in a temperature range of 100°C or higher and 250°C or lower. Examples of the fluorine-containing group that detaches at a temperature range of 100°C or higher and 250°C or lower include those bonded to the polymer via an acetal bond, hemiacetal bond, thioacetal bond, sulfur hemiacetal bond, etc. Fluorine-based and so on. Among them, in terms of obtaining higher smoothness and increasing the wettability of the surface after heating, it is preferable to include one selected from the following general formula (1-1) and the following general formula (1-2) More than one structure.

(In general formula (1-1) and general formula (1-2), L ¹ represents an oxygen atom or a sulfur atom, R ¹ , R ² and R ³ each independently represent a hydrogen atom, and the number of carbon atoms that may have a substituent is 1 or more and 18 or less hydrocarbon groups, R _f represents an alkyl group having a fluorine atom or a polyalkylene ether group having a fluorine atom; R ¹ and R _f may be bonded to form a ring structure)

It is estimated that when the above-mentioned thermally decomposable fluoropolymer contains one or more structures selected from the above-mentioned general formula (1-1) and the above-mentioned general formula (1-2), the fluorine-containing polymer containing R _f is heated by heating. The group is detached, and a hydroxyl group or a carboxyl group is generated at the end of the polymer side, for example. On the other hand, it is estimated that the boiling point of the detached fluorine-containing group is relatively low, and it is difficult to remain on the surface of the colored layer due to volatilization or the like. As a result, it is inferred that the hydrophilicity and lipophilicity of the surface of the colored layer after heating are both improved, and the wettability is improved.

Examples of the hydrocarbon group having 1 or more and 18 or less carbon atoms of R ¹ , R ² and R ³ include: an alkyl group having 1 or more and 18 or less carbon atoms, an alkyl group having 7 or more carbon atoms, and An aralkyl group having 18 or less, an aryl group having 6 or more and 18 or less carbon atoms, etc.

基、異

基、二環戊基、金剛烷基、低級烷基取代金剛烷基等。 The above-mentioned alkyl group may be any of linear, branched, and cyclic, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl,

Base, different

Group, dicyclopentyl, adamantyl, lower alkyl substituted adamantyl, etc.

As said aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, and it may have a substituent further.

Moreover, as said aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned, and it may have a substituent further.

Examples of the substituent that the alkyl group of the above-mentioned alkyl group and the above-mentioned aralkyl group may have include halogen atoms such as F, Cl, and Br, and a hydroxyl group. In addition, examples of the substituent of the aromatic ring possessed by the aryl group and the aralkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms, halogen atoms, and hydroxyl groups.

Furthermore, the above preferred carbon number does not include the carbon number of the substituent.

In the embodiment of the present invention, R ¹ to R ^{3 are} particularly preferably each independently a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably each independently a hydrogen atom, A methyl group or an ethyl group is more preferably each independently a hydrogen atom or a methyl group, and it is particularly preferable that R ¹ to R ³ are all hydrogen atoms.

The alkyl group having a fluorine atom in R _{f should} just be an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. As the alkyl group, an alkyl group having 1 or more and 18 or less carbon atoms is preferable, and an alkyl group having 10 or less carbon atoms is preferable. In the alkyl group having a fluorine atom, the number of carbon atoms to which the fluorine atom is directly bonded is 1 or more, but in terms of smoothness, the number of carbon atoms to which the fluorine atom is directly bonded is preferably 4 or more. Furthermore, in terms of the environment, in the alkyl group having a fluorine atom, the number of carbon atoms to which the fluorine atom is directly bonded is preferably 6 or less.

The alkyl group may be any one of linear, branched, and cyclic, and specific examples include alkyl groups in which at least one hydrogen atom is substituted with a fluorine atom, which is the same as the ^{above-mentioned R 1} to R ^3. In R _f , it is preferable that at least 4 hydrogen atoms are substituted with fluorine atoms.

In addition, _{the polyalkylene ether group having a fluorine atom in R f may} be a polyalkylene ether group in which at least one hydrogen atom is substituted with a fluorine atom. As the polyalkylene ether group, for example ^{, a group represented by -R 4} -(OR ⁴ ) _m -OR ^4' , etc. (m is an integer of 0 or more and 17 or less, R ⁴ is a carbon atom number of 1 or more and 6 or less of alkylene, R ^{4 'is} a number of 1 or more carbon atoms and an alkyl group of 6 or less, there are a plurality of R ⁴ may be the same or different from each other).

Examples of the alkylene group of R ⁴ include: methylene, ethylene, propylene, etc. As the substituent, in addition to a fluorine atom, a chlorine atom, a bromine atom, an alkyl group, etc. may be included as the substitution The alkyl group of the group may further have a fluorine atom as a substituent. Further, as the R ^{4 'of} the alkyl group include: methyl, ethyl, propyl, etc., as a substituent, a fluorine atom, but may also have a chlorine atom, a bromine atom.

The term R ¹ and R _{f are} bonded to form a ring structure means that R ¹ and R _f form a ring structure via L ^1. In this case, at least one fluorine atom is required in the ring structure.

As a preferable _{structure of R f} , the following can be mentioned, for example, but it is not limited to these.

(m, m', n and n'are each independently an integer from 1 to 18)

In the above formula, n is preferably 2 or more, more preferably 4 or more. On the other hand, it is preferably 12 or less, more preferably 8 or less, and still more preferably 6 or less.

In the above formula, n'is preferably 2 or more, on the other hand, it is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.

In the above formula, m is preferably 2 or more, more preferably 4 or more, on the other hand, it is preferably 10 or less, and more preferably 8 or less.

In the above formula, m'is preferably 2 or more, more preferably 4 or more, on the other hand, it is preferably 8 or less, and more preferably 6 or less.

Moreover, in the embodiment of the present invention, the thermally decomposable fluoropolymer preferably has a structural unit represented by the following general formula (2).

(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 represented by the above general formula (1-1) or the above general formula (1-2) Substituents indicated)

In the present invention, the so-called L ² being 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 of L 2} is not particularly limited as long as Q1 can be linked to the carbon atom of the main chain skeleton. As ^{the divalent linking group of L 2} , for example, a linear, branched or cyclic alkylene group, (-COO-L ³ -(L ³ is a linear, branched or cyclic alkylene group) )) etc., the alkylene group may further have an oxy group (-O-) in the carbon chain. Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group. As the substituent, in addition to a fluorine atom, a chlorine atom, a bromine atom, an alkyl group, and the like may be included.

In the embodiment of the present invention, L ^{2 is} particularly preferably a direct bond or (-COO-L ³ -).

In the present invention, the production method of the thermally decomposable fluoropolymer is not particularly limited. For example, in the case of manufacturing a thermally decomposable fluoropolymer containing one or more structures selected from the above general formula (1-1) and the above general formula (1-2), it can be selected from hydroxyl and After introducing a compound represented by the following general formula (3) into a polymerizable monomer with one or more substituents in the carboxyl group to prepare a fluorine-containing monomer, the monomer is polymerized with other monomers as needed. It is a fluorine-containing polymer having a structural unit containing a fluorine-containing group. In addition, a structural unit having one or more substituents selected from a hydroxyl group and a carboxyl group, and a polymer having other structural units as necessary, can also be prepared. One or more substituents selected from hydroxyl and carboxyl groups in the polymer are introduced into the compound represented by the following general formula (3), whereby the structural unit having one or more substituents selected from hydroxyl and carboxyl groups becomes The structural unit containing a fluorine-containing group is thus made into a fluorine-containing polymer. Furthermore, the above-mentioned hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group.

[化6]

(The symbols in the general formula (3) are the same as the above general formula (1-1) and the above general formula (1-2))

In the embodiment of the present invention, the thermally decomposable fluoropolymer may be a polymer containing a fluorine-containing group-containing structural unit, or may be a copolymer having a fluorine-containing group-containing structural unit and other structural units. Among them, it is preferable to have other structural units in terms of compatibility with other components of the coloring composition, solubility in solvents, and the like.

When the thermally decomposable fluoropolymer is a copolymer having a structural unit containing a fluorine-containing group and other structural units, the copolymer may be a random copolymer, or may have a structural unit containing a fluorine-containing group The block copolymer of the block portion and the block portion containing other structural units may also be the graft copolymer described below.

As other structural units possessed by the thermally decomposable fluoropolymer, structural units derived from monomers having unsaturated double bonds can be appropriately selected and used. Examples of monomers having unsaturated double bonds include (meth)acrylic acid, (meth)acrylates, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Specific examples include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate , Isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, hexyl (meth)acrylate, chloroethyl (meth)acrylate, allyl (meth)acrylate, (meth) Benzyl acrylate, butoxyethyl (meth)acrylate, butoxyethylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, (methyl) ) 2-ethylhexyl acrylate, Glyceryl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, isobornyl (meth)acrylate, (former Base) isodecyl acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxy Glycol (meth)acrylate, phenoxyethyl (meth)acrylate, stearyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate Base ester, biphenoxyethyl acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, trimethylolpropane mono(meth)acrylate, polyoxyisobutyl monobutyl (Meth) acrylates such as ether (meth)acrylate; (meth)acrylamide, N-alkyl (meth)acrylamide, N,N-dialkyl (meth)acrylamide (Alkyl is methyl, ethyl or propyl), tert-butyl(meth)acrylamide, N-hydroxyethyl-N-methyl(meth)acrylamide, N-2-acetamide Aminoethyl-N-acetyl (meth)acrylamide and other (meth)acrylamides; allyl acetate, allyl hexanoate, allyl laurate, allyl palmitate, hard Allyl esters such as allyl fatty acid, allyl benzoate, allyl acetate, allyl lactate or allyl compounds such as allyloxyethanol; hexyl vinyl ether, octyl vinyl ether, decyl Vinyl ether, ethylhexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethyl propyl vinyl ether, 2 -Ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylamino ethyl vinyl ether, diethylamino ethyl vinyl ether, butylamino ethyl vinyl ether, benzyl ethylene Vinyl ethers such as ether and tetrahydrofurfuryl vinyl ether; vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl caproate, chloroacetic acid Vinyl ester, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl lactate, vinyl β-phenyl butyrate, cyclohexyl Vinyl esters such as vinyl carboxylate.

(Graft copolymer)

In the embodiment of the present invention, the thermally decomposable fluoropolymer preferably has the above general formula (2) in terms of compatibility with other components of the coloring composition or solubility in solvents, etc. A graft copolymer of the structural unit shown and the structural unit represented by the following general formula (4).

(In the general formula (4), L ⁴ represents a direct bond or a divalent linking group, R ⁶ represents a hydrogen atom or a methyl group, and the polymer represents a polymer selected from the following general formula (5) and the following general formula (6) And one or more polymer chains in the following general formula (7))

(In the general formula (5), R ⁸ is a hydrogen atom or a methyl group, and 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] _x1 -R ¹² , -[(CH ₂ ) _y1 -O] _z1 -R ¹² , -[CO- (CH ₂ ) _y1 -O] _z1 -R ¹² , -CO-OR ¹³ or -O-CO-R ¹⁴ Represents a monovalent group, R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a methyl group, R ¹² is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or -CH ₂ COOR ¹⁵ , a monovalent group, R ¹³ is a hydrocarbyl group, -[CH(R ¹⁰ )-CH(R ¹¹ )-O] _x2 -R ¹² , -[(CH ₂ ) _y2 -O] _z2 -R ¹² , -[CO-(CH ₂ ) _y2 -O] _z2- A monovalent group represented by R ^{12 , R 14} is a hydrocarbon group with 1 or more and 18 or less ^{carbon atoms, and R 15} is a hydrogen atom or one with 1 or more and 5 or less carbon atoms Alkyl, the above-mentioned hydrocarbyl group may have a substituent; R ⁸ and R ⁹ that exist in plural may be the same as or different from each other; n represents an integer of 5 or more and 200 or less; x1 and x2 represent an integer of 1 or more and 18 or less, y1 And y2 represent an integer from 1 to 5, z1 and z2 represent an integer from 1 to 18; in the general formula (6), m'represents an integer from 1 to 5, and n'represents an integer from 3 to 200 Integer, there are plural m's which may be the same or different; in the general formula (7), R ¹⁶ and R ¹⁷ each independently represent a linear or branched alkylene with 2 or more and 8 or less carbon atoms Base, m" and n" are each independently an integer of 0 or more and 200 or less, and the total of m" and n" is 5 or more and 200 or less)

The ^{divalent linking group of L 4} includes, for example, linear, branched or cyclic alkylene, linear, branched or cyclic alkylene having a hydroxyl group, arylalkylene, and -CONH- Group, -COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), and combinations thereof. Among them, L ^{4 is} preferably a divalent linking group including -COO- group or -CONH- group.

As ^{the hydrocarbon group of R 9} , R ¹² , R ¹³ , and R ¹⁴ , an alkyl group having 1 or more and 18 or less carbon atoms, an alkenyl group or an aralkyl group having 2 or more and 18 carbon atoms are preferable基 or aryl.

基、異

基、二環戊基、金剛烷基、低級烷基 取代金剛烷基等。 The above-mentioned alkyl group having 1 or more and 18 or less carbon atoms may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, N-butyl, tertiary butyl, cyclopentyl, cyclohexyl,

Base, different

Group, dicyclopentyl, adamantyl, lower alkyl substituted adamantyl, etc.

The alkenyl group having 2 or more and 18 or less carbon atoms may be linear, branched, or cyclic. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group, etc. are mentioned, for example.

As said aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of 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 biphenylmethyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of 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.

In addition, as the substituent of the aromatic ring such as the aryl group or aralkyl group, in addition to the linear or branched alkyl group having 1 to 4 carbon atoms, alkenyl and nitro Radicals, halogen atoms, etc.

Furthermore, the above-mentioned 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 integers of 1 or more and 4 or less, more preferably integers of 1 or more and 2 or less, y1 and y2 are integers of 1 or more and 5 or less, preferably 1 An integer of above and below 4 is more preferably 2 or 3. z1 and z2 are an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, and more preferably an integer of 1 or more and 2 or less.

In addition, the number n of the structural unit of the polymer chain is not particularly limited as long as it is an integer of 5 to 200, and it is preferably in the range of 5 to 100.

In the embodiment of the present invention, in terms of compatibility with the following binder components, R ⁹ is preferably -CO-OR ¹³ . Specific examples of the preferred R ¹³ in the preferred R ⁹ include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, hexyl, and chloroethyl , Allyl, benzyl, butoxyethyl, butoxyethoxy, cyclohexyl, dicyclopentyl, 2-ethylhexyl, glyceryl, glycidyl, 2-hydroxyethyl, 2- Hydroxypropyl, isobornyl, isodecyl, isooctyl, lauryl, 1-adamantyl, 2-methoxyethyl, methoxyethoxy, phenoxyethyl, stearyl, Dodecyl, tridecyl, biphenoxyethyl, furfuryl, tetrahydrofurfuryl, trimethylolpropyl, polyoxyisobutyl monobutyl, etc., but not limited to these .

In the 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. In addition, the number n'of the structural unit of the polymer chain is not particularly limited as long as it is an integer of 3 to 200, and it is preferably in the range of 5 to 100.

In the general formula (7), R ¹⁶ and R ¹⁷ each independently represent a straight or branched chain alkylene group having 2 or more and 8 or less carbon atoms, and R ¹⁶ and R ¹⁷ have different structures from each other. . Specific examples of R ¹⁶ and R ¹⁷ include: ethylene, ethylene (trimethylene), methyl ethylene, butyl (tetramethylene), dimethylethylene, ethyl Ethylene, 1-methyl ethylene, pentylene, propyl ethylene, hexylene, butyl ethylene, heptylene, octylene, etc.

m" and n" are each independently an integer of 0 or more and 200 or less, and the total of m" and n" is 5 or more and 200 or less. When m" or n" is 0, it means 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, and it is preferably 5 or more and 50 or less. Furthermore, ^{the repeating unit containing R 16 and} the repeating unit containing R ¹⁷ can be randomly arranged in random copolymerization, and ^{the repeating unit containing R 16 and} the repeating unit containing R ¹⁷ can be alternately arranged in alternating copolymerization. It may also be a block copolymerization having a block containing a repeating unit of ^{R 16} and a block containing a repeating unit of ^{R 17.}

As a preferred specific example of the general formula (7), there can be mentioned: m" is 5 or more, n" is 0, and R ¹⁶ is a polypropylene oxide in which methyl ethylene is; m" is 5 or more, and n" is 0 , R ¹⁶ is poly 1,3-propylene glycol of trimethylene; m" is 5 or more, n" is 0, R ¹⁶ is polybutylene oxide of ethyl ethylene; m" is 5 or more, n" is 0 , R ¹⁶ is tetramethylene poly-1,4-butanediol; m" and n" are both at least 1, R ¹⁶ is ^{ethylene oxide and R 17} is methyl ethylene oxide and ring Copolymer of propylene oxide; both m" and n" are 1 or more, R ¹⁶ is methyl ethylene, R ¹⁷ is ethyl ethylene copolymer of propylene oxide and 1,2-butylene oxide; m Both "and n" are 1 or more, R ¹⁶ is an ethylene group, and R ¹⁷ is a copolymer of ethylene oxide and tetrahydrofuran in which tetramethylene is used.

In the case of having a polymer chain represented by general formula (6) or general formula (7), the terminal of the polymer chain is not particularly limited. Examples of the terminal of the polymer chain represented by the general formula (6) or (7) include a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group constituting the terminal include the same ones as the above-mentioned hydrocarbon groups of R ⁹ , R ¹² , R ¹³ , and R ¹⁴ . In the embodiment of the present invention, as the terminal of the polymer chain represented by the general formula (6) or the general formula (7), a hydrogen atom or an alkyl group is preferred, and a hydrogen atom or a carbon atom number of 1 is preferred. A linear or branched alkyl group with at least one and at most eight. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, and octyl.

The mass average molecular weight Mw of the polymer chain of the polymer is preferably in the range of 350 to 20,000, more preferably in the range of 500 to 10,000. By being in the above range, the compatibility with other components is excellent.

In addition, as a standard for the polymer chain of the polymer, it is preferable that the solubility at 23° C. is 50 (g/100g solvent) or more relative to the solvent used in combination.

When the thermally decomposable fluoropolymer is a copolymer having structural units containing thermally decomposable fluorine-containing groups and other structural units, the ratio of structural units containing thermally decomposable fluorine-containing groups is combined It is not particularly limited. Based on the entire structural unit constituting the thermally decomposable fluoropolymer, the fluorine-containing group-containing structural unit is preferably 5 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 50 mass% %the following.

The mass average molecular weight Mw of the thermally decomposable fluoropolymer is preferably in the range of 1,000 to 100,000, more preferably in the range of 5,000 to 70,000 in terms of good compatibility with other resins. In addition, the number average molecular weight Mn of the thermally decomposable fluoropolymer is preferably in the range of 1,000 to 50,000, and more preferably in the range of 1,500 to 20,000 in terms of good compatibility with other resins.

In the present invention, the mass average molecular weight Mw and the number average molecular weight Mn are values measured by GPC (Gel Permeation Chromatography). The measurement was performed in the following manner: HLC-8220GPC manufactured by Tosoh was used, the elution solvent was N-methylpyrrolidone (NMP) with 0.01 mol/L lithium bromide added, and the polystyrene standard used for the calibration curve was 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) (the above are manufactured by Tosoh), and the measurement column is TSK-GEL ALPHA-M×2 (manufactured by Tosoh).

In the present invention, the method of confirming that the fluoropolymer is a pyrolyzable fluoropolymer in which fluorine is desorbed in a temperature range of 100°C or higher and 250°C or lower is not particularly limited.

For example, measure the content of fluorine atoms in the fluorine-containing polymer heated to 100°C and the content of fluorine atoms in the fluorine-containing polymer heated to 250°C. If heated to If the content of fluorine atoms in the fluoropolymer after 250°C is less than the content of fluorine atoms in the fluoropolymer heated to 100°C, it is confirmed that the fluorine content is based on the temperature range above 100°C and below 250°C. The thermal decomposition type fluoropolymer.

In addition, it can also be confirmed by the following method that it is a thermally decomposable fluoropolymer that contains fluorine in a temperature range of 100°C or higher and 250°C or lower: Gas Chromatography Mass Spectrometry (GCMS) in a temperature region below 250°C detected thermal decomposition products derived from fluorine-containing groups.

The method for measuring the content of fluorine atoms in the fluoropolymer is not particularly limited, and for example, fluorescent X-ray analysis can be used.

The content of fluorine atoms of the thermally decomposable fluoropolymer after heating to 250° C. is preferably 30% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less. The reason for this is that if it is less than the above upper limit value, the wettability of the surface of the obtained colored layer is high, and the coating layer is easily formed on the surface.

(A) Pigment

In the coloring composition of the present invention, the (A) colorant contains a salt-forming colorant of dye. In the present invention, the so-called salt-forming colorant of the dye refers to a dispersible dye that is made into a dispersible dye by using a well-known lakeing (chlorination) method to make the dye insoluble in a solvent, and the dispersibility is achieved by the following dispersant Improve, and heat resistance or light resistance is also improved. The coloring composition of the present invention uses the above-mentioned (D) fluorine-containing polymer and the salt-forming colorant of the dye in combination to suppress the color fading in the color filter manufacturing step and obtain a high-brightness coloring layer.

As the chlorinated dye, it can be appropriately selected from previously known dyes. Examples of such dyes include: azo dyes, metal complex salt azo dyes, anthraquinone dyes, triarylmethane dyes, dibenzopyran dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, Methyl dyes, phthalocyanine dyes, etc.

The salt-forming colorant of the dye can be obtained, for example, by mixing the dye and a compound having a desired counter ion in a solvent.

As the coloring layer formed by using the coloring composition of the present invention, in terms of forming a protective layer without an ultraviolet cleaning step, etc., as the colorant (A), a coloring material selected from those suitable for high brightness can be preferably used. One or more of triarylmethane-based colorants and dibenzopyran-based colorants that are liable to decrease brightness due to ultraviolet radiation.

In the embodiment of the present invention, the triarylmethane dyes used for chlorination can be appropriately selected from known ones, for example: CI Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72, CI Acid Blue 1, 3, 5, 7, 9, 19, 22, 83, 90, 93, 100, 103, 104, 109, CI Acid Green 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 18, 22, 50, 50:1 and other triarylmethane acid dyes; CI basic violet 1, 3, 14, CI basic blue 1, 5, 7, 8 , 11, 26, CI basic green 1, 4 and other triarylmethane-based basic dyes.

In addition, the dibenzopyran dyes used for chlorination can be appropriately selected from known ones, for example: CI Acid Red 50, 51, 52, 87, 92, 94, 289, 388, CI Acid Red Violet 9, 30, 102, sulforhodamine G, sulforhodamine B, sulforhodamine 101, sulforhodamine 640 and other dibenzopyran acid dyes; CI basic violet 11 and other dibenzopyran Furan series basic dyes, etc.

Among the dibenzopyran-based acid dyes, Rhodamine-based acid dyes such as C.I. Acid Red 50, C.I. Acid Red 52, C.I. Acid Red 289, C.I. Acid Violet 9, C.I. Acid Violet 30, and C.I. Acid Blue 19 are preferred.

In addition to metal ions, the relative cations of the salt-forming pigments of acid dyes include organic cations and inorganic polymers. The metal ion is preferably an ion having a valence of 2 or higher, and examples thereof include calcium ion, barium ion, aluminum ion, copper ion, and iron ion. The organic cation is not particularly limited. Examples include: containing an amine group, a pyridyl group, an imidazole group, etc., which can form a salt with an anion The organic compound of the functional group can be colorless, and also known basic dyes can be used. As the organic cation, among them, a quaternary ammonium cation or a quaternary phosphonium cation is preferred. As the inorganic polymer, polyaluminum chloride or zirconium oxychloride can be preferably used.

On the other hand, the relative anion of the salt-forming color material of the basic dye is not particularly limited, and it may be an organic anion or an inorganic anion. As a specific example of the organic anion, the one described in the International Publication No. 2012/144520 pamphlet can be cited. In addition, as an inorganic anion, for example, anions of an oxo acid having a valence of two or more (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ) Etc.) or inorganic anions such as polyacid ions formed by condensation of multiple oxo acids or mixtures thereof.

In the present invention, as the dibenzopyran-based colorant, in terms of excellent heat resistance of the colorant and formation of a high-brightness coating film, among them, the salt-forming colorant of rhodamine-based acid dyes is preferred Among them, the salt-forming colorant of rhodamine-based acid dyes having the structure represented by the following general formula (II) is more preferable.

(In the general formula (II), R ²¹ to R ²⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R ²¹ and R ²² , R ²³ and R ²⁴ can be bonded to form a ring structure; R ²⁵ represents a halogen atom, an optionally substituted alkyl group, a sulfonate group (-SO ₃ ^- group) or a carboxylate ^{group (-COO-} group); m represents 0 ~5, when R ²⁵ is plural, there are plural R ²⁵ which may be the same or different from each other; R ²⁶ and R ²⁷ each independently represent a hydrogen atom, a halogen atom or an alkyl group which may have a substituent; wherein, R ²¹ ~ R ²⁵ have at least two acidic groups or their salts, and one of them forms an intramolecular salt)

The alkyl groups of R ²¹ to R ²⁴ include, for example, linear or branched alkyl groups having 1 to 12 carbon atoms. Among them, linear or branched alkyl groups having 1 to 8 carbon atoms are preferred. , In terms of brightness and heat resistance, it is more preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Among them, ^{the alkyl group of R 21} to R ²⁴ is particularly preferably an ethyl group or a methyl group. The substituents that the alkyl group may have are not particularly limited, and examples include aryl groups, halogen atoms, hydroxyl groups, sulfonate groups (-SO ₃ ^- groups)-containing substituents, and carboxylate ^{groups (-COO-} groups). The substituents of) and the like, examples of the substituted alkyl group include benzyl and the like, which may further have a sulfonate group or a carboxylate group.

The aryl group of R ²¹ to R ²⁴ includes, for example, an aryl group having 6 to 12 carbon atoms. Specific examples of the aryl group include, for example, a phenyl group, a naphthyl group, and the like. Examples of the substituent that the aryl group may have include an alkyl group, a halogen atom, etc., and the alkyl group may further have a sulfonate group or a carboxylate group.

Examples of the aralkyl group of R ²¹ to R ²⁴ include aralkyl groups having 7 to 16 carbon atoms. Specific examples include benzyl, phenethyl, naphthylmethyl, biphenylmethyl, etc. Furthermore, it has a sulfonate group or a carboxylate group.

啉環等。 The so-called R ²¹ and R ²² , R ²³ and R ^{24 being} bonded 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. The ring structure is not particularly limited, and examples include: pyrrolidine ring, piperidine ring,

Morpholino ring and so on.

The alkyl group of R ²⁶ and R ²⁷ may be the same as the alkyl group of ^{R 21} to R ^{24 described above.} In addition, ^{examples of the halogen atom of R 26} and R ²⁷ include a fluorine atom, a chlorine atom, and a bromine atom.

R ²⁵ represents a halogen atom, an optionally substituted alkyl group, a sulfonate group (-SO ₃ ^- group), or a carboxylate ^{group (-COO-} group). Examples of the alkyl group which may have a substituent include ^{the same alkyl groups as the above-mentioned R 21} to R ²⁴ , which may have a sulfonate group or a carboxylate group.

In the above general formula (II), ^{the substitution position of the substituent R 25} of the benzene ring bonded to the dibenzopyran skeleton is preferably relative to the dibenzopyran skeleton in terms of stability Ortho position or para position, more preferably ortho position. If the substituent R ²⁵ is in the ortho position, it is presumed that it can resonate with the carbon atom of the dibenzopyran skeleton to which the benzene ring is bonded to form a ring structure, and therefore the heat resistance is improved.

Among the rhodamine-based acid dyes represented by the above general formula (II), it is preferable that ^{at least one of R 21} , R ²² , R ²³ and R ²⁴ is an aryl group or a heteroaryl group in terms of improving heat resistance . Particularly in terms of improving heat resistance, it is preferable that 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. When at ^{least one of R 21} , R ²² , R ²³ and R ²⁴ is an aryl group or a heteroaryl group, it is inferred that ^{at least one of R 21} , R ²² , R ²³ and R ²⁴ is bound by the nitrogen atom The lone electron pair not only resonates with the dibenzopyran skeleton, but also resonates with the aryl or heteroaryl group, so that the molecule is more stabilized.

Specific examples of the acidic group or a salt thereof, the include: a carboxyl group (-COOH), a carboxylate (-COO ^-), carboxylate groups (-COOM, where M represents a metal atom), a sulfonate (-SO ₃ ^-), a sulfo group (-SO ₃ H), sulfonate groups (-SO ₃ M, where M represents a metal atom), wherein, preferably having a sulfonate (-SO ₃ ^-), a sulfo group At least one of (-SO ₃ H) or sulfonate group (-SO _{3 M).} Furthermore, as the metal atom M, sodium atom, potassium atom, etc. can be mentioned.

The rhodamine-based acid dye represented by the general formula (II) is in R ²¹ to R ²⁵ and has at least two acidic groups or their salts in one molecule, one of which forms an intramolecular salt, and R is preferred. ²⁵ has one acidic group, ^{at least one of R 22} and R ²³ has an acidic group, more preferably at least one of R ²² and R ²³ has an aryl group with an acidic group. It is preferable in terms of effectively proceeding the reaction between the acidic group and the cationic species by making the acidic group exist in a separate position within 1 molecule.

Specific examples of rhodamine-based acid dyes represented by the general formula (II) include: acid red 50, 52, 289, sulforhodamine G, acid violet 9, 30, anion of acid blue 19, etc., such as Rhodamine The salt-forming color of Ming-based acid dyes has excellent heat resistance and can form a high-brightness coating film. In terms of easy availability, acid red 52, 289 is preferred.

As a salt-forming pigment of rhodamine-based acid dyes, it is particularly preferably the metal of rhodamine-based acid dyes described in International Publication No. 2015/059962 in terms of excellent heat resistance and forming a high-brightness coating film. Lake color.

In addition, in the coloring composition of the present invention, in terms of the colorant having excellent heat resistance and forming a high-brightness coating film, it is preferable that the colorant (A) contains the following general formula (I) Color material.

(In the general formula (I), A is an organic group with a valence of a carbon atom directly bonded to N without a π bond. The organic group means that at least the terminal directly bonded to N has a saturated aliphatic hydrocarbon group and is in the carbon chain It may contain O, S, N aliphatic hydrocarbon groups, or the end directly bonded to N has aliphatic hydrocarbon groups and the carbon chain may contain O, S, N aromatic groups, R ⁱ , R ⁱⁱ , R ⁱⁱⁱ , R ^iv and R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may be bonded to form a ring structure; R ^vi and R ^vii each Independently represent an optionally substituted alkyl group or an optionally substituted alkoxy group, Ar ⁱ represents an optionally substituted divalent aromatic group, B ^c- represents a c-valent anion, and a and c represent 2 or more Integer, b and d represent an integer of 1 or more, e represents 0 or 1, f and g represent an integer of 0 or more and 4 or less, f+e and g+e are 0 or more and 4 or less, and there are plural R ⁱ ~ R ^vii , Ar ⁱ , e, f and g may be the same or different)

In A, as an aliphatic hydrocarbon group with at least a saturated aliphatic hydrocarbon group at the end directly bonded to N, if the carbon atom at the end directly bonded to N does not have a π bond, it can be linear, branched or cyclic In either case, the carbon atoms other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain may contain O, S, and N. For example, it may contain a carbonyl group, a carboxyl group, an oxycarbonyl group, an amido group, etc., and the hydrogen atom may be further substituted with a halogen atom or the like.

In addition, in A, the above-mentioned aromatic group having an aliphatic hydrocarbon group includes: a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to at least N, which may have a substituent , It can be a heterocyclic ring containing O, S, and N.

Among them, in terms of the fastness of the skeleton, A is preferably a cyclic aliphatic hydrocarbon group or an aromatic group.

烷、雙環[2.2.2]辛烷、三環[5.2.1.0^2,6]癸烷、金剛烷等。 Examples of cyclic aliphatic hydrocarbon groups include: cyclohexane, cyclopentane, and

Alkanes, bicyclo[2.2.2]octane, tricyclo[5.2.1.0 ^2,6 ]decane, adamantane, etc.

烷、雙環[2.2.2]辛烷、三環[5.2.1.0^2,6]癸烷、金剛烷等。又，作為芳香族基，例如可列舉：含有苯環、萘環之基，其中，較佳為含有苯環之基。 The cyclic aliphatic hydrocarbon group is preferably a bridged alicyclic hydrocarbon group in terms of the fastness of the skeleton. The so-called bridged alicyclic hydrocarbon group refers to a polycyclic aliphatic hydrocarbon group having a bridged structure and a polycyclic structure in the aliphatic ring, for example:

Alkanes, bicyclo[2.2.2]octane, tricyclo[5.2.1.0 ^2,6 ]decane, adamantane, etc. 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 ease of obtaining raw materials, A is preferably 2 to 4 valences, preferably 2 to 3 valences, and more preferably 2 valences. For example, when A is a divalent organic group, examples include linear, branched or cyclic alkylene groups with 1 to 20 carbon atoms, or xylylene groups substituted with 2 carbon atoms The aromatic group of 1~20 alkylene, etc.

The alkyl group of R ⁱ to R ^v is not particularly limited. For example, a straight or branched chain alkyl group with 1 to 20 carbon atoms can be cited. Among them, a straight chain or branched chain alkyl group with 1 to 8 carbon atoms is preferred for easy manufacturing and raw material supply. In terms of properties, it is more preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Among them, ^{the alkyl group of R i} to R ^v is particularly preferably ethyl or methyl. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group, and examples of the substituted alkyl group include a benzyl group.

The aryl group of R ⁱ to R ^v is not particularly limited. For example, a phenyl group, a naphthyl group, etc. are mentioned. Examples of the substituent that the aryl group may have include an alkyl group, a halogen atom, and the like, and examples of the aryl group that has a substituent include a tolyl group and a xylyl group.

In ^{the case where at least one of R ii} to R ^v is an aryl group, compared with the case of an alkyl group, the heat resistance of the colorant is excellent, but on the other hand, there is a tendency for light resistance to deteriorate. However, the embodiment of the present invention does not require an ultraviolet cleaning step in the manufacturing step of the color filter. Therefore, in this embodiment, it is preferable that ^{at least one of R ii} to R ^v is an aryl group.

啉環等。 The so-called R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^{v are} bonded to form a ring structure means that R ⁱⁱ and R ⁱⁱⁱ , and R ^iv and R ^v form a ring structure via a nitrogen atom. The ring structure is not particularly limited, and examples include: pyrrolidine ring, piperidine ring,

Morpholino ring and so on.

啉環。 Among them, in terms of chemical stability, R ⁱ to R ^{v are} preferably each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v bond to form pyrrolidine ring, piperidine ring,

Morpholino ring.

R ⁱ ~ R ^v can form the above-mentioned structures independently, and among them, in terms of color purity, R ⁱ is preferably a hydrogen atom, and further, in terms of ease of manufacturing and raw material supply, R is more preferred. ⁱⁱ ~ R ^v are the same or R ⁱⁱ and R ^{v are the} same and R ⁱⁱⁱ and R ^{iv are the} same.

R ^vi to R ^vii each independently represent an optionally substituted alkyl group or an optionally substituted alkoxy group. The alkyl group of R ^vi to R ^vii is not particularly limited, but is preferably a linear or branched alkyl group having 1 or more and 8 or less carbon atoms, more preferably 1 or more and 4 or less carbon atoms之alkyl. Examples of the alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be linear or branched.

In addition, ^{the alkoxy group of 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 more preferably 1 carbon atom. Above and 4 or less alkoxy groups. Examples of the alkoxy group having 1 or more and 4 or less carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, which may be linear or branched.

The ^{number of substitutions of R vi} to R ^vii , that is, f and g each independently represent an integer of 0 or more and 4 or less, and among them, 0 or more and 2 or less are preferable, and 0 or more and 1 or less are more preferable.

In addition, R ^vi to R ^vii can be substituted at any position of the aromatic ring having a resonance structure in the triarylmethane skeleton or the dibenzopyran skeleton, and among them, it is preferable to use -NR ⁱⁱ R ⁱⁱⁱ or -NR ^{The amine group represented by iv} R ^v is the base meta-substitution.

唑、噻唑、咪唑、吡唑等5員雜環；吡喃、哌咔、吡啶、哌咔、嗒

、嘧啶、吡

等6員雜環；苯并呋喃、苯并噻吩、吲哚、咔唑、香豆素、苯并哌咔、喹啉、異喹啉、吖啶、酞

、喹唑啉、喹

啉等縮合多環式雜環。該等芳香族基可具有上述R^vi~R^vii之可具有取代基之烷基或可具有取代基之烷氧基作為取代基。 The ^{divalent aromatic group of Ar i} is not particularly limited. The aromatic group may be a heterocyclic group in addition to the aromatic hydrocarbon group containing a carbocyclic ring. As the aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to the benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetrahydronaphthalene ring, indene ring, stilbene ring, anthracene ring, phenanthrene ring, etc.; biphenyl, biphenyl Chain polycyclic hydrocarbons such as triphenyl, diphenylmethane, triphenylmethane, and stilbene. In the chain polycyclic hydrocarbon, it is also possible to have O, S, and N in the chain skeleton such as diphenyl ether. On the other hand, as the heterocyclic ring in the heterocyclic group, furan, thiophene, pyrrole,

5-membered heterocycles such as azole, thiazole, imidazole, pyrazole; pyran, pipercarb, pyridine, pipercarb, da

, Pyrimidine, pyridine

6-member heterocycles; benzofuran, benzothiophene, indole, carbazole, coumarin, benzopipercarb, quinoline, isoquinoline, acridine, phthalein

, Quinazoline, quine

Condensation of polycyclic heterocycles with morpholines and the like. Such aromatic groups may have the above R ^vi ~ R ^vii of an optionally substituted alkyl group or an alkoxy group of a substituent of the group as a substituent.

^{The anion (B c-} ) having a valence of two or more is not particularly limited, and it may be an organic anion or an inorganic anion. As these anions, the same relative anions as those of the salt-forming color material of the above-mentioned basic dyes can be appropriately selected and used.

In the embodiment of the present invention, as an anion with a valence of 2 or higher, in terms of the heat resistance or light resistance of the colorant, a polyacid anion containing at least one of tungsten and molybdenum is preferred, and among them, a polyacid anion is more preferred. Contains polyacid anions of tungsten. Colorants with polyanions containing tungsten are particularly excellent in heat resistance, but on the other hand, there is a tendency for light resistance to deteriorate. However, the embodiment of the present invention does not require an ultraviolet cleaning step in the manufacturing step of the color filter. Therefore, in this embodiment, it is preferable to use a polyanion containing tungsten with excellent heat resistance.

As a specific example of the polyacid anion containing at least one of tungsten and molybdenum, for example, Cochin 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- , Kojin-type tungstosilicate ion α-[SiW ₁₂ O ₄₀ ] ⁴ -, β-[SiW ₁₂ O ₄₀ ] ^4- , Γ-[SiW ₁₂ O ₄₀ ] ^4- , and further examples include: [P ₂ W ₁₇ O ₆₁ ] ^10- , [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 ₁₁ 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- , [Mo ₈ O ₂₆ ] ^4- and so on.

As an anion of an inorganic acid containing molybdenum and/or tungsten, in terms of heat resistance and light resistance and ease of obtaining raw materials, among the above, heteropoly acid is preferred, and more preferably contains P (phosphorus) heteropoly acid.

(Other pigments)

In the embodiment of the present invention, the coloring composition may further contain other colorants within a range that does not impair the effect. Other color materials are adjusted as needed for the purpose of controlling the color tone. In the coloring composition of this embodiment, other colorants are not particularly limited as long as they can achieve the desired color development when forming the coloring layer. Various organic pigments, inorganic pigments, and dyes can be used alone or in combination of two or more. Wait. Among them, organic pigments are better used due to their higher color rendering properties and higher heat resistance. Examples of organic pigments include compounds classified as pigments in the color index (C.I.; issued by The Society of Dyers and Colourists), and specific examples include those with a color index (C.I.) number as follows.

As other coloring materials, the following coloring materials can be mentioned, for example, but it is not limited to these.

CI Pigment Violet 1, CI Pigment Violet 2, CI Pigment Violet 3, CI Pigment Violet 19, CI Pigment Violet 23; CI Pigment Blue 1, CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60, CI Pigment Red 81, CI Pigment Red 82 and other pigments or acid red and other dyes.

As the blending amount of other color materials, relative to 100 parts by mass of the total amount of the (A) color materials, the other color materials are preferably 40 parts by mass or less, more preferably 20 parts by mass or less. The reason is that if the range is Inner, the color tone can be controlled without damaging the high transmittance characteristics of the salt-forming pigments of the above-mentioned dyes.

(B) Dispersant

In the coloring composition of the present invention, the colorant is dispersed in a solvent by a dispersant for use. As a dispersing agent, those previously used as dispersing agents can be appropriately selected and used. As specific examples of the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, fluorine, and other surfactants can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable in terms of uniform and fine dispersion. These dispersants can be used singly or in combination of two or more.

Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid, (parts) Ammonium or (part of) alkylamine salts; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates or modified products thereof; polyurethanes; unsaturated Polyamides; Polysiloxanes; Long-chain polyamino amide phosphates; Polyethyleneimine derivatives (by the combination of poly(lower alkyleneimine) and polyester containing free carboxyl groups The amide or the base obtained by the reaction); polyallylamine derivative (the co-condensate of polyallylamine and selected from polyester with free carboxyl group, polyamide or ester and amide ( Polyesteramide), the reaction product obtained by the reaction of more than one of the three compounds), etc.

As a commercially available product of such a dispersant, for example, Disperbyk-2000, 2001, BYK-LPN6919, 21116 (manufactured by BYK-Chemie‧Japan), Ajisper PB821, 881 (manufactured by Ajinomoto), etc. Among them, in terms of heat resistance, electrical reliability, and dispersibility, BYK-LPN6919 and 21116 are preferred.

As a polymer dispersant, among them, the above-mentioned pigments can be dispersed and the dispersion stability is better On the good side, it is preferably selected from a polymer having at least a structural unit represented by the following general formula (III), and a urethane bond (-NH- COO-) is one of the group consisting of urethane-based dispersants of compounds.

Hereinafter, the above-mentioned preferred dispersants will be described in detail.

<Polymer having at least the structural unit represented by the following general formula (III)>

In the embodiments of the present invention, a polymer having at least a structural unit represented by the following general formula (III) can be preferably used as a dispersant.

(In the general formula (III), R ³¹ represents a hydrogen atom or a methyl group, L ⁵ represents a direct bond or a divalent linking group, and Q ² represents a group represented by the following general formula (III-a) or may have a substituent The nitrogen-containing heterocyclic group that can form a salt)

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

In the general formula (III), L ⁵ is a direct bond or a divalent linking group. The so-called direct bond means that Q ² is directly bonded to the carbon atom of the general formula (III) without a linking group.

As ^{the divalent linking group of L 5} , 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 are mentioned. (-R'-OR"-: R'and R" are each independently an alkylene group) and combinations thereof.

Among them, in terms of dispersibility, L ⁵ in the general formula (III) is preferably a direct bond, a divalent linking group including a -CONH- group or a -COO- group.

Moreover, it can be used especially preferably by making the structural unit represented by the said general formula (III) of these dispersing agents form a salt in arbitrary ratios using the following salt forming agents.

As a polymer having a structural unit represented by the general formula (III), among them, it improves the dispersibility and dispersion stability of the colorant and the heat resistance of the resin composition to form a high-brightness and high-contrast colored layer. In other words, it is preferably a block copolymer having the structure described in WO2011/108495, JP 2013-054200, JP 2010-237608, and JP 2011-75661 And graft copolymers.

Moreover, as a commercial product of the polymer which has the structural unit represented by general formula (III), BYK-LPN6919 etc. are mentioned.

≪Salt forming agent≫

In the embodiment of the present invention, a preferable dispersant is a polymer in which at least a part of the nitrogen site of the structural unit represented by the general formula (III) forms a salt (hereinafter sometimes referred to as salt modification).

In the present invention, by using a salt forming agent to form a salt on the nitrogen part of the structural unit represented by the general formula (III), the dispersant strongly adsorbs the colorant that also forms the salt, thereby improving The dispersibility and dispersion stability of the pigment. As the salt forming agent, acidic organophosphorus compounds, organic sulfonic acid compounds, quaternary agents, etc. described in WO2011/108495 and JP 2013-054200 can be preferably used. In particular, when the salt forming agent is an acidic organophosphorus compound, the salt forming site containing the acidic organophosphorus compound of the dispersant locally exists on the surface of the particles of the colorant, whereby the colorant surface becomes a state of being coated with phosphate, so The attack (hydrogen abstraction) on the dye skeleton of the colorant caused by active oxygen is suppressed, and the heat resistance or light resistance of the dye skeleton-containing colorant is improved. Therefore, if a polymer modified with a salt of an acidic organophosphorus compound is used as a dispersant, the high-transmittance colorant used in the present invention can be further inhibited from fading during high-temperature heating in a state where the high-transmittance colorant used in the present invention is well dispersed. Even after the high-temperature heating step in the color filter manufacturing step, a higher-brightness colored layer can be formed.

<Urethane Dispersant>

A urethane-based dispersant that can be preferably used as a dispersant is a dispersant containing a compound having more than one urethane bond (-NH-COO-) in one molecule.

By using a urethane-based dispersant, it can be dispersed well in a small amount. By using a small amount of the dispersant, the blending amount of the hardening component and the like can be relatively increased, and as a result, a colored layer with excellent heat resistance can be formed.

In the present invention, as the urethane-based dispersant, among them, (1) polyisocyanates having two or more isocyanate groups in one molecule, and (2) selected from single-terminal or both-terminal polyisocyanates are preferred. A reaction product of one or more of polyesters having hydroxyl groups and poly(meth)acrylates having hydroxyl groups at one or both ends, and more preferably (1) polyisocyanates having two or more isocyanate groups in one molecule Type, and (2) one or more selected from polyesters having hydroxyl groups at one or both ends and poly(meth)acrylates having hydroxyl groups at one or both ends, and (3) having one or more in the same molecule The reaction product of active hydrogen and basic or acidic compounds.

Commercially available urethane-based dispersants include: Disperbyk-161, 162, 163, 164, 167, 168, 170, 171, 174, 182, 183, 184, 185, BYK-9077 (above (Manufactured by BYK-Chemie‧Japan), Ajisper PB711 (manufactured by Ajinomoto), EFKA-46, 47, 48 (manufactured by EFKA CHEMICALS), etc. Among them, in terms of heat resistance, electrical reliability, and dispersibility, Disperbyk-161, 162, 166, 170, and 174 are preferred.

In the coloring composition of the present invention, the content of the (B) dispersant is not particularly limited as long as it can uniformly disperse the (A) colorant. The (A) colorant has excellent dispersibility and dispersion stability and can be stored In terms of excellent stability, it is preferably 1% by mass or more, and more preferably 5% by mass or more with respect to the total solid content of the coloring composition. In addition, in terms of improving developability, the content of the (B) dispersant relative to the total solid content of the coloring composition is preferably 50% by mass or less, more preferably 40% by mass or less, and more Preferably, it is 30% by mass or less.

Furthermore, a dispersing agent can be used individually by 1 type or in combination of 2 or more types.

(C) Adhesive ingredients

The coloring composition of the present invention contains a binder component in order to impart film-forming properties or adhesion to the coated surface. Among them, in order to impart sufficient hardness to the coating film, it is preferable to contain a curable adhesive component. The curable adhesive component is not particularly limited, and a conventionally known curable adhesive component for forming the colored layer of a color filter can be suitably used.

As the curable adhesive component, for example, a photocurable adhesive component containing a photocurable resin that can be polymerized and cured by visible light, ultraviolet rays, electron beams, etc., or a heat-curable adhesive component that can be polymerized and cured by heating can be used. It is a thermosetting adhesive component of curable resin.

For example, in the case of using the coloring composition of the present invention in an inkjet method, etc., when the coloring layer can be selectively attached in a pattern on the substrate, the curable adhesive component does not need to be developed sex. In this case, the well-known thermosetting adhesive component or photosensitive adhesive component used in the case of forming the colored layer of the color filter by an inkjet method or the like can be suitably used.

As a thermosetting adhesive, 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 that can promote the thermosetting reaction can be added. Examples of thermosetting functional groups include epoxy groups, oxetanyl groups, isocyanate groups, and ethylenically unsaturated bonds. As the thermosetting functional group, an epoxy group is preferably used. As a specific example of a thermosetting adhesive component, for example, those described in International Publication No. 2012/144521 can be cited.

On the other hand, when a photolithography step is used when forming a coloring layer, it is preferable to use a photosensitive adhesive component having alkali developability.

Hereinafter, the photosensitive adhesive component will be described, but the curable adhesive component is not limited to these. In addition to the photosensitive adhesive components described below, thermosetting adhesive components such as epoxy resins that can be polymerized and hardened by heating can be used.

As the photosensitive binder component, a positive photosensitive binder component and a negative photosensitive binder component can be mentioned. Examples of the positive photosensitive binder component include a system containing an alkali-soluble resin and a compound containing an o-quinonediazide group as a photosensitive imparting component.

On the one hand, as a negative photosensitive adhesive component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator can be preferably used.

In the coloring composition of the present invention, a negative photosensitive adhesive component is preferred in terms of the fact that patterns can be easily formed by photolithography using an existing process.

Hereinafter, the alkali-soluble resin, polyfunctional monomer, and photoinitiator constituting the negative photosensitive adhesive components will be specifically described.

(1) Alkali-soluble resin

In the embodiment of the present invention, if the alkali-soluble resin has an acidic group and functions as a binder resin, and is soluble in the developer used in pattern formation, particularly preferably the alkaline developer, it may be appropriate Choose to use.

The preferred alkali-soluble resin in the embodiment of the present invention is preferably a resin having a carboxyl group as an acidic group, and specific examples thereof include acrylic copolymers having carboxyl groups, epoxy (meth)acrylate resins having carboxyl groups, and the like. Among these, 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 are particularly preferred. The reason for this is that by containing a photopolymerizable functional group, the film strength of the formed cured film is improved. In addition, these acrylic copolymers and epoxy acrylate resins can be used in combination of two or more types.

The acrylic copolymer with a carboxyl group is obtained by copolymerizing a carboxyl-containing ethylenic unsaturated monomer and an ethylenic unsaturated monomer.

The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocyclic system 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 inhibits the alkali solubility of the coloring composition, but also functions as a component that improves the solubility to the solvent and further the solvent re-solubility.

Specific examples of acrylic copolymers having a carboxyl group include, for example, those described in International Publication No. 2012/144521, and specific examples include: including methyl (meth)acrylate and (meth)acrylic acid A copolymer of a monomer having no carboxyl group such as ethyl ester and one or more selected from (meth)acrylic acid and anhydrides thereof. In addition, for example, an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group and a hydroxyl group may be added to the above-mentioned copolymer to introduce an ethylenically unsaturated bond polymer, etc., but it is not limited In these.

Among these, it can be polymerized with the following polyfunctional monomers during exposure to make the colored layer become In terms of more stability, it is particularly preferable to introduce an ethylenically unsaturated bond by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer or the like.

The copolymerization ratio of the carboxyl-containing ethylenically unsaturated monomer in the carboxyl-containing copolymer is usually 5-50% by mass, preferably 10-40% by mass. In this case, if the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the resulting coating film will be less soluble in alkaline developing solutions, making it difficult to form a pattern. In addition, if the copolymerization ratio exceeds 50% by mass, there is a tendency for the pattern to be formed to fall off from the substrate or the film on the surface of the pattern is likely to be rough during development with an alkaline developer.

The preferred 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 function of the adhesive after curing is significantly reduced, and if it exceeds 500,000, it may be difficult to form a pattern during development with an alkaline developer. In addition, the mass average molecular weight is obtained by gel permeation chromatography (GPC) as a standard polystyrene conversion value.

The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, but it is preferably an epoxy (methyl) obtained by reacting a reactant of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride Acrylate compound.

Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected and used from known ones. As a specific example, for example, those described in International Publication No. 2012/144521, etc. can be cited. The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride may be used singly, or two or more may be used in combination.

The alkali-soluble resin used in the embodiment of the present invention can be used alone or in combination of two or more. As its content, relative to 100 parts by mass of the colorant contained in the coloring composition, it is usually 10~1000 mass. In the range of parts, preferably in the range of 20~500 parts by mass Inside. 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 colorant may be relatively low, and a sufficient coloring concentration may not be obtained.

(2) Multifunctional monomer

The polyfunctional monomer used in the embodiment of the present invention is not particularly limited as long as it can be polymerized by the following photoinitiator. Generally, a compound having two or more ethylenically unsaturated double bonds is used. Particularly preferred is a multifunctional (meth)acrylate having two or more acrylic or methacrylic groups.

As such a polyfunctional (meth)acrylate, what is necessary is just to select it suitably from the conventionally well-known thing. As a specific example, for example, those described in International Publication No. 2012/144521, etc. can be cited.

These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when the coloring composition of the present invention is required to have excellent photocuring properties (high sensitivity), the multifunctional monomer is preferably one having 3 (trifunctional) or more polymerizable double bonds, preferably Poly(meth)acrylates of polyhydric alcohols with three or more valences or modified products of these dicarboxylic acids, specific examples include: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylic acid Ester, succinic acid modified product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate Modified succinic acid of meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(2-(meth)acryloyloxyethyl) phosphate, tris(2-(meth)propylene) An oxypropyl) ester and the like are preferable.

The total content of the above-mentioned polyfunctional monomers used in the coloring composition of the present invention is not particularly limited, and is usually about 5 to 500 parts by mass relative to 100 parts by mass of the alkali-soluble resin. Preferably it is the range of 20-300 mass parts. If the content of the multifunctional monomer is less than the above range, photocuring may not proceed sufficiently and the exposed part may be eluted. If the content of the multifunctional monomer exceeds the above range, the alkali developability may decrease.

(3) Photoinitiator

The photoinitiator used in the coloring composition of the present invention is not particularly limited, and one or two or more of the previously known photoinitiators can be used in combination. As a specific example, for example, those described in International Publication No. 2012/144521 can be cited.

The content of the photoinitiator used in the coloring composition of the present invention is generally about 0.01-100 parts by mass, preferably 5-60 parts by mass, relative to 100 parts by mass of the above-mentioned polyfunctional monomer. If the content is less than the above range, the hardness of the colored layer may not be sufficient because the polymerization reaction cannot be sufficiently generated. On the other hand, if the content is more than the above range, the color in the solid component of the coloring composition may be present. The content of materials, etc., is relatively small, and sufficient coloring density cannot be obtained.

(E) Solvent

In the embodiment of the present invention, the solvent can be appropriately selected and used from solvents that do not react with the components in the coloring composition and can dissolve or disperse them. Specific examples include: alcohol series; ether alcohol series; ester series; ketone series; ether alcohol acetate series; ether series; aprotic amide series; lactone series; unsaturated hydrocarbon series; saturated hydrocarbon series and other organic solvents, Among them, it is preferable to use an ester-based solvent in terms of solubility during dispersion and coating suitability.

Preferred ester solvents include, for example, methyl methoxypropionate, ethyl ethoxypropionate, ethyl methoxyacetate, propylene glycol monomethyl ether acetate, 3-methoxy-3- Methyl-1-butyl acetate, 3-methoxy butyl acetate, methoxy butyl acetate, ethoxy ethyl acetate, ethyl cellosolve acetate, dipropylene glycol methyl ether acetate, propylene glycol Diacetate, 1,3-butanediol diacetic acid Ester, cyclohexanol acetate, 1,6-hexanediol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.

Among them, it is preferable to use propylene glycol monomethyl ether acetate (PGMEA) in terms of low risk to the human body, low volatility near room temperature, and excellent heat drying properties. In this case, there is the following advantage: no special cleaning step is required when switching from the previous coloring composition with PGMEA.

These solvents can be used alone or in combination of two or more.

(Optionally add ingredients)

In the embodiments of the present invention, various additives may be contained as needed within a range that does not impair the purpose.

Examples of additives include antioxidants, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.

Specific examples of surfactants and plasticizers include, for example, those described in International Publication No. 2012/144521.

In terms of heat resistance and light resistance, it is preferable that the coloring composition further contains an antioxidant. The antioxidant can be appropriately selected from those previously known. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc. In terms of heat resistance, it is preferable to use Hindered phenolic antioxidants.

The so-called hindered phenol-based antioxidant refers to an antioxidant having a structure containing at least one phenol structure and substituted with a substituent with a carbon number of 4 or more on at least one of the 2-position and the 6-position of the hydroxyl group of the phenol structure. In addition, it may also be a latent antioxidant in which hindered phenolic hydroxyl groups are protected by a protective group as described in Japanese Patent Laid-Open No. 2015-132791 and become latent.

(The mixing ratio of each component in the coloring composition)

Preferably, the total content of the (A) colorant containing the dye-containing salt-forming colorant and other colorants is 5-65% by mass relative to the total solid content of the coloring composition, more preferably 8-55% by mass Proportional deployment. If the colorant is too small, the penetration density may be insufficient when the coloring composition is applied to a specific film thickness (usually 1.0~5.0μm), and if the coloring material is too large, the coloring composition may be coated. The adhesiveness to the substrate, the surface roughness of the cured film, the hardness of the coating film, etc. as the characteristics of the coating film may become insufficient when it is applied to the substrate and cured. The ratio of the amount of dispersant used for the dispersion of the material has also increased, so the characteristics such as solvent resistance may become insufficient. Furthermore, in the present invention, the solid components are all components other than the above-mentioned solvents, and also include polyfunctional monomers dissolved in the solvents and the like.

The content of the (B) dispersant is not particularly limited as long as the colorant can be uniformly dispersed. For example, 10 to 150 parts by mass can be used with respect to 100 parts by mass of the colorant. Furthermore, it is preferable to mix it in the ratio of 15-100 mass parts with respect to 100 mass parts of color materials, and it is especially preferable to mix it in the ratio of 15-70 mass parts. The total content of the dispersant is preferably in the range of 1-60% by mass relative to the total solid content of the coloring composition, and preferably in the range of 5-50% by mass. When the above content is less than 1% by mass relative to the total solid content of the coloring composition, it may be difficult to uniformly disperse the colorant. When it exceeds 60% by mass, it may cause a decrease in curability and developability. Yu.

It is preferable that (C) the binder component is formulated in a ratio of 5 to 90% by mass, preferably 10 to 80% by mass, relative to the total amount of the solid content of the coloring composition.

It is preferable that the (D) fluorine-containing polymer is formulated in a ratio of 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass, relative to the total solid content of the coloring composition.

In addition, the content of (E) solvent is not particularly limited as long as the colored layer can be formed with high accuracy. Certainly. Relative to the total amount of the aforementioned coloring composition containing the solvent, it is usually preferably in the range of 65 to 95% by mass, and preferably in the range of 75 to 88% by mass. By making the content of the above-mentioned solvent within the above-mentioned range, it is possible to have excellent coatability.

(Manufacture of coloring composition)

As a method of producing the coloring composition, for example: (1) First, prepare a colorant dispersion liquid containing at least (A) colorant, (B) dispersant and (E) solvent, and put in the colorant dispersion liquid at the same time, ( C) Adhesive components, (D) fluorine-containing compounds and various additives used according to the needs and mixing methods, (2) adding (C) adhesive components, (D) fluorine-containing compounds and mixing them in the solvent A method of adding and mixing the above-mentioned colorant dispersion liquid after mixing the various additives used.

In addition, the above-mentioned colorant dispersion can be prepared by mixing and stirring the (B) dispersant in the (E) solvent, and after preparing the dispersant solution, mixing the (A) colorant in the dispersant solution and if necessary For other compounds, use a dispersing machine to disperse them. Moreover, it can also be prepared by mixing a colorant and a dispersant in a solvent, and dispersing them using a known dispersing machine.

Examples of dispersing machines for dispersing colorants include: roller mills such as two-roll mills and three-roll mills, ball mills such as ball mills, vibratory ball mills, paint conditioners, continuous disc type bead mills, and continuous ring Type bead mill and other bead mills. As a preferable dispersion condition of the bead mill, the diameter of the beads used is preferably 0.03~2.00mm, more preferably 0.05~1.0mm.

Specific examples include: pre-dispersing with 2mm zirconia beads with a larger bead diameter, and then performing formal dispersion with 0.1mm zirconia beads with a smaller bead diameter. Furthermore, it is preferable to filter with a membrane filter of 0.1 to 2.0 μm after dispersion.

2. Color filter

The color filter of the embodiment of the present invention is a color with a colored layer on a transparent substrate In the optical filter, at least one of the colored layers is a cured product of the colored composition of the present embodiment.

The color filter according to the embodiment of the present invention will be described with reference to the drawings. Fig. 1 and Fig. 2 are respectively schematic cross-sectional views showing an embodiment of a color filter. The color filter 10 shown in the example of FIG. 1 has a transparent substrate 1, a light-shielding portion 2 and a coloring layer 3. In addition, the color filter 10 shown in the example of FIG. 2 has a transparent substrate 1, a light-shielding portion 2 and a colored layer 3, and further has a coating layer 4 on the colored layer 3.

In the color filter of the present invention, at least one of the colored layers is a hardened product of the coloring composition of the present invention, so it has high brightness, high smoothness, and excellent surface wettability. In addition, when it has a coating layer, it becomes a color filter that suppresses unevenness of the coating film of the coating layer.

(Colored layer)

In the color filter of the embodiment of the present invention, at least one of the colored layers is the cured product of the coloring composition of the present embodiment described above.

The colored layer is usually formed in the opening of the light-shielding portion on the transparent substrate described below, and usually contains a colored pattern of more than three colors.

In addition, the arrangement of the colored layer is not particularly limited, and it may be, for example, a normal arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type. In addition, the width and area of the colored layer can be arbitrarily set.

The thickness of the colored layer can be appropriately controlled by adjusting the coating method, the solid content concentration or viscosity of the colored composition, etc., and is usually preferably in the range of 1 to 5 μm.

(Shading part)

The color filter of the embodiment of the present invention may have a light-shielding portion. The shading part is attached to the following What is formed in a pattern on the bright substrate can be the same as what is used as a light-shielding part in a normal color filter.

The pattern shape of the light-shielding portion is not particularly limited, and examples include shapes such as a stripe shape and a matrix shape. Examples of the light-shielding portion include those obtained by dispersing or dissolving a black pigment in a binder resin, or metal thin films such as chromium and chromium oxide. The metal thin film can be a _{two-layer stack of CrO x} film (x is any number) and Cr film, and it can also be a CrO _x film (x is any number), CrN _y film (y Any number) and three layers of Cr film.

When the light-shielding part is formed by dispersing or dissolving a black colorant in a binder resin, as a method of forming the light-shielding part, it is not particularly limited as long as it is a method that can pattern the light-shielding part. For example, the photolithography method, the printing method, the inkjet method, etc. which use the colored resin composition for light-shielding parts are mentioned.

The film thickness of the light-shielding part is set to about 0.2~0.4μm in the case of a metal thin film, and set to about 0.5~2μm when the black colorant is dispersed or dissolved in the binder resin.

(Transparent substrate)

The transparent substrate of the color filter according to the embodiment of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and the transparent substrate used in ordinary color filters can be used. Specific examples include: non-flexible transparent rigid materials such as quartz glass, alkali-free glass, synthetic quartz plates, or transparent soft materials with flexibility or softness such as transparent resin films, optical resin plates, and flexible glass.

The thickness of the transparent substrate is not particularly limited. According to the use of the color filter of the present invention, for example, about 50 μm to 1 mm can be used.

Furthermore, the color filter of the present invention can remove the above-mentioned transparent substrate, light-shielding part, and coloring layer. In addition, for example, a top coating layer or a transparent electrode layer is also formed, and an alignment film useful for aligning the liquid crystal material, or a columnar spacer, etc. are formed. The color filter of the present invention is not limited to the above-exemplified configuration, and a known configuration used in general color filters can be appropriately selected and used.

(Coating layer)

The color filter of the embodiment of the present invention may optionally have a coating layer on the colored layer. In this embodiment, the coating layer is not particularly limited, and is appropriately selected from various layers or films that can usually be provided on the colored layer as needed. As the coating layer, for example, in addition to a protective layer that protects the colored layer, a transparent conductive layer such as an alignment film (alignment layer) or an ITO (Indium Tin Oxides) film can also be cited.

In the color filter of the present embodiment, at least one of the colored layers is the cured product of the coloring composition of the present invention, so regardless of the coating layer, it can be a coating layer without unevenness.

When the above-mentioned covering layer is a protective layer, the protective layer only needs to be a layer transparent to visible light, and it can be appropriately selected from organic protective layers used in ordinary color filters, preferably containing resin The protective layer.

The resin for the protective layer may be appropriately selected from those previously known, and may be a thermoplastic resin, or a cured product of a thermosetting or light-curing resin.

The method of forming the protective layer is not particularly limited, but it is preferable to use the following protective layer composition. As described above, the coloring layer formed by using the coloring composition of the present invention has a tendency that the acidic group or the hydroxyl group after the fluorine-containing group is separated from the above-mentioned fluorine-containing polymer is easily exposed on the surface. Therefore, the hydrophilicity and lipophilicity of the surface of the colored layer become higher, and the composition for the protective layer can be coated without unevenness.

Furthermore, when a protective layer is formed as a coating layer in this embodiment, the above-mentioned alignment film or the above-mentioned transparent conductive layer may be further provided on the protective layer.

Also, in this embodiment, a transparent conductive layer can be adjacent to the colored layer as a coating Floor.

<Composition for protective layer>

The composition for a protective layer contains at least a resin that becomes the protective layer, and usually contains a solvent, and may further contain other components as necessary.

As the resin contained in the composition for a protective layer, what is generally used as a transparent protective layer of a color filter can be used, and it may be a thermosetting composition or a photocuring composition. As the photocurable composition, a composition containing the above-mentioned polyfunctional monomer and the above-mentioned photoinitiator may be mentioned, and may further contain acrylic resin, styrene resin, novolac resin, maleic acid resin, Binder resins such as rosin resins.

On the other hand, in the embodiments of the present invention, especially in terms of reducing the number of times of light irradiation, a thermosetting composition is preferred.

As a thermosetting composition, a combination of a compound having a thermosetting functional group and a curing agent is usually used, and a catalyst that promotes the thermosetting reaction can be added, and it can also contain others that can react or not react with the thermosetting functional group. Resin component.

In the embodiment of the present invention, as described above, there is a tendency that acidic groups or hydroxyl groups are easily exposed on the surface of the colored layer. Therefore, in terms of excellent adhesion to the colored layer, it is preferable to use a compound having an epoxy group As a compound with a thermosetting functional group.

As the compound having an epoxy group, an epoxy compound having two or more epoxy groups in one molecule is preferable. The epoxy compound having 2 or more epoxy groups in a molecule is an epoxy compound having 2 or more epoxy groups in a molecule, preferably 2 to 50, and more preferably 2 to 20 epoxy groups (including Those who are epoxy resin). The epoxy group should just be a structure which has an oxirane ring structure, for example, a glycidyl group, an epoxycyclohexyl group, etc. are illustrated. Examples of epoxy compounds include well-known polyvalent epoxy compounds that can be hardened by carboxylic acids. Such epoxy compounds are widely disclosed in, for example, Shinpo These can be used in the "Epoxy Resin Handbook" Nikkan Kogyo Shimbun (1987) edited by Masaki.

As said epoxy compound, the polymer containing the monomer containing epoxy groups, such as glycidyl (meth)acrylate, may be mentioned preferably, and it may be a copolymer with the other monomer which does not have an epoxy group, for example.

In addition, as the epoxy compound called epoxy resin, it is preferably one containing two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bromine Bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, sulphur type ring Oxygen resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, trihydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenol ethane type epoxy resin, bicyclic Pentadiene phenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A core-containing polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine Type epoxy resin, glyoxal type epoxy resin, alicyclic type epoxy resin, heterocyclic type epoxy resin, etc.

The curing agent used in the thermosetting composition can be appropriately selected and used from known curing agents. Examples of hardeners include amines, imidazoles, polycarboxylic acids, polycarboxylic acid anhydrides, and polycarboxylic acids with blocked carboxyl groups.

The above-mentioned other resin components are components contained for the purpose of improving the heat resistance or scratch resistance of the protective layer, etc., and can be appropriately selected from those previously known. For example, polyester amide acid or organosilane condensate (organic-inorganic hybrid type) obtained by reacting tetracarboxylic dianhydride and diamine with a high hydroxyl compound can be used.

In addition, the above-mentioned composition for a protective layer may further contain well-known additives such as antioxidants, leveling agents, silane coupling agents, and chain transfer agents, if necessary.

In addition, the alignment film used as the coating layer is a layer for aligning the liquid crystal compound in a certain direction. In this embodiment, the alignment film is preferably formed using a composition for alignment film.

The composition for an alignment film can be appropriately selected and used from previously known ones. For example, it can be applied: Lecithin, silane-based surfactants, titanate-based surfactants, pyridinium salt-based polymer surfactants, n-octadecyltriethoxysilane and other silane coupling-based alignment membrane compositions , Soluble polyimide with long-chain alkyl or alicyclic structure in the side chain or polyimide-based alignment film composition such as polyimide with long-chain alkyl or alicyclic structure in the side chain .

3. Manufacturing method of color filter

The method of manufacturing a color filter of an embodiment of the present invention is a method of manufacturing a color filter with a colored layer on a transparent substrate, and it includes the following steps: step (i), which forms the above-mentioned embodiment on a transparent substrate The coating film of the coloring composition in the form; step (ii), which is to harden the above-mentioned coating film; and step (iii), which is to heat the hardened coating film.

The above-mentioned color filter manufacturing method uses the above-mentioned coloring composition of the present embodiment. Therefore, the surface wettability can be improved without irradiating the cured coating film of the coloring composition with ultraviolet rays, so that a color that suppresses the decrease in the brightness of the colored layer can be produced Filter.

The manufacturing method of the present invention has at least the above-mentioned steps (i) to (iii), if necessary, it may further have the step (iv) of forming a coating layer on the colored layer, or pre-installed on the above-mentioned transparent substrate by the above-mentioned method Steps of the above-mentioned shading part, etc. Hereinafter, each step will be described, and each component in the coloring composition and each configuration of the color filter are as described above, so the description is omitted here.

(Step (i))

The method of forming the coating film of the colored composition of the above embodiment is not particularly limited, and may be The same method as the usual color filter manufacturing method. For example, coating methods such as spray coating, dip coating, bar coating, roll coating, and spin coating are used to coat the transparent substrate to form a wet coating film. Then, if necessary, drying is performed by a known method such as heating to remove the solvent in the coloring composition.

(Step (ii))

The step of hardening the coating film obtained in the above step (i) can be appropriately selected from known methods according to the binder component in the coloring composition. In the hardening step, at least it changes to a state that does not show fluidity. For example, when the coloring composition is a photosensitive coloring composition and the coloring layer is arranged in a pattern, exposure is carried out through a photomask of a specific pattern, and the alkali-soluble resin and polyfunctional monomer are subjected to photopolymerization. , Thereby hardening the above-mentioned coating film in a pattern. As a light source used for exposure, ultraviolet rays, electron beams, etc., such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, are mentioned, for example. The amount of exposure can be appropriately adjusted according to the light source used or the thickness of the coating film.

Next, a developing solution is used to perform a development process to dissolve and remove the unexposed part, thereby forming a hardened coating film with a desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of surfactant and the like can be added to the alkaline solution. Also, as the development method, a usual method can be used.

After the development treatment, the developer is usually washed and the hardened coating film of the coloring composition is dried to form a colored layer. Furthermore, after the development treatment, a heating treatment may be performed to sufficiently harden the coating film. The heating conditions are not particularly limited, and can be appropriately selected according to the application of the coating film.

(Step (iii))

The method of heating the cured coating film is not particularly limited, but it is preferably at a temperature higher than the temperature at which the fluorine-containing group is released from the thermally decomposable fluorine-containing polymer contained in the coloring composition of the present invention. Heat at temperature.

Specifically, it is preferable to heat at 100°C or higher, more preferably at 150°C or higher, and still more preferably at 200°C or higher. The upper limit of the temperature can be appropriately adjusted in consideration of the heat resistance of the colorant, etc., and is usually 350°C or lower, preferably 280°C or lower. In addition, the heating time can be appropriately adjusted according to the thickness of the cured coating film, etc., and is usually 5 minutes or more and 120 minutes or less, preferably 10 minutes or more and 60 minutes or less.

By this step (iii), the fluorine-containing group is detached from the above-mentioned (D) fluorine-containing polymer. Therefore, the hydrophilicity and lipophilicity of the surface of the colored layer can be improved without the ultraviolet cleaning step before the coating layer is formed. , The wettability of the surface becomes excellent.

For example, when the colored layers of three colors are arranged in a pattern, a coloring composition is prepared for each color, and these are set as the first coloring composition, the second coloring composition, and the third coloring composition, respectively. The above-mentioned steps (i) to (iii) are repeated for each coloring composition, thereby obtaining the pattern-shaped hardened coating film. In the case of this example, it is preferably between the step (iii) of the first coloring composition and the step (i) of the second coloring composition, and the step (iii) and the step (iii) of the second coloring composition Between the step (i) of the third coloring composition, there is no ultraviolet cleaning step. By not having an ultraviolet cleaning step, the brightness drop caused by the deterioration of the color material can be suppressed.

Furthermore, the above is the case where the three-color coloring layer is arranged in a pattern as an example, and when the coloring layer is two colors and the coloring layer is four or more colors, the patterned coloring layer is formed in the same way.

(Step (iv))

When a coating layer is provided on the colored layer, it is preferable to perform step (iv) after the above step (iii). It is particularly preferable that there is no ultraviolet cleaning step between the above step (iii) and the above step (iv). By not having an ultraviolet cleaning step, the brightness drop caused by the deterioration of the color material can be suppressed.

The method of forming the coating layer can be appropriately selected from previously known methods according to the type of the coating layer. For example, when the covering layer is the above-mentioned protective layer or the above-mentioned alignment film, it is preferable to use the above-mentioned protective layer composition or the above-mentioned alignment film composition in terms of suppressing unevenness of the protective layer and the like, by It is formed by the same method as the step of forming the hardened coating film of the colored composition described above.

In the case of forming an alignment film as a coating layer, after the hardened coating film is formed by the above-mentioned method, the alignment film can be made by applying an alignment restriction force to the alignment film. As a method of imparting an alignment restriction force to the alignment film, for example, a conventionally known method such as a rubbing method or a photo-alignment method can be used. Furthermore, in the present invention, the so-called alignment restriction force refers to the interaction that causes the liquid crystal compound on the alignment film to be aligned in a specific direction.

In addition, when the coating layer is a transparent conductive layer such as the above-mentioned ITO film, it can be appropriately selected from conventionally known methods such as electron beam vapor deposition, physical vapor deposition, and sputtering.

[Liquid crystal display device]

The liquid crystal display device of the embodiment of the present invention includes the color filter of the embodiment of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

The liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 3 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As shown in FIG. 3, the liquid crystal display device 40 of this embodiment has: a color filter 10, a counter substrate 20 having a TFT (thin-film transistor) array substrate, etc., and a color filter formed on the The liquid crystal layer 15 between the sheet 10 and the above-mentioned counter substrate 20. The example illustrated in FIG. 3 is: an alignment film 13a is formed on the side of the protective layer 5 formed on the coloring layer 3 of the color filter 10 and an alignment film 13b is formed on the side of the counter substrate 20, the two alignment films 13a and 13b A liquid crystal layer 15 is formed therebetween. Furthermore, the example illustrated in FIG. 3 is: the liquid crystal display device 40 has: a polarizing plate 25a arranged on the outer side of the color filter 10 and a counter substrate The polarizing plate 25b arranged on the outer side of the liquid crystal display device 40, and the backlight 30 arranged on the outer side of the polarizing plate 25b arranged on the side of the counter substrate 20 of the liquid crystal display device 40.

Furthermore, the liquid crystal display device of this embodiment is not limited to the configuration shown in FIG. 3, and may be a generally known configuration as a liquid crystal display device using color filters.

The driving method of the liquid crystal display device of this embodiment is not particularly limited, and a driving method generally used in a liquid crystal display device can be adopted. Examples of such driving methods include: TN (Twisted Nematic) method, IPS (In-Plane Switching, transverse electric field drive) method, OCB (optically compensated bend) method, and MVA (Multi- Domain Vertical Alignment, multi-domain vertical alignment) method and so on. In this embodiment, any of these methods can be preferably used.

In addition, as the counter substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention and the like.

Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used in accordance with the driving method of the liquid crystal display device of the present embodiment and the like.

As a method for forming the liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, for example, a vacuum injection method or a liquid crystal dropping method can be cited.

In the vacuum injection method, for example, a color filter and a counter substrate are used to make a liquid crystal cell in advance, the liquid crystal is heated to make an isotropic liquid, and the capillary effect is used to inject the liquid crystal into the liquid crystal cell in an isotropic liquid state , Sealed with an adhesive, whereby a liquid crystal layer can be formed. After that, the liquid crystal cell is slowly cooled to normal temperature, so that the enclosed liquid crystal can be aligned.

In addition, in the liquid crystal dropping method, for example, a sealant is applied to the edge of the color filter, the color filter is heated until the liquid crystal becomes the temperature of the isotropic phase, and the dispensing machine is equal to the state of the isotropic liquid Drop liquid crystals, overlap the color filter and the counter substrate under reduced pressure, and pass through By adhering the sealant, the liquid crystal layer can be formed. After that, the liquid crystal cell is slowly cooled to normal temperature, so that the enclosed liquid crystal can be aligned.

In addition, the backlight used in the liquid crystal display device of this embodiment can be appropriately selected according to the use of the liquid crystal display device. As a backlight, for example, in addition to cold cathode fluorescent tubes (CCFL: Cold Cathode Fluorescent Lamp), white LED (light-emitting diode, light-emitting diode), white organic EL (Electroluminescence, electroluminescence) as The backlight unit of the light source.

Examples of white LEDs include: a combination of red LEDs, green LEDs and blue LEDs to obtain white light, and a combination of blue LEDs, red LEDs and green phosphors to obtain white light. The white LED, the white LED that obtains white light by mixing the blue LED with the red light-emitting phosphor and the green light-emitting phosphor, the white light is obtained by the color mixing of the blue LED and the YAG-based phosphor White LEDs, white LEDs that obtain white light by combining ultraviolet LEDs with red light-emitting phosphors, green light-emitting phosphors, and blue light-emitting phosphors. As the above-mentioned phosphor, quantum dots can be used.

[Light-emitting display device]

The light-emitting display device of the embodiment of the present invention has the color filter and the luminous body of the above-mentioned embodiment of the present invention. As the light-emitting display device of the present invention, for example, an organic light-emitting display device having an organic light-emitting body as the light-emitting body can be cited. The light-emitting body is not limited to an organic light-emitting body, and an inorganic light-emitting body can also be suitably used.

The light-emitting display device of this embodiment will be described with reference to the drawings. Fig. 4 is a schematic diagram showing an example of the light-emitting display device of this embodiment. As shown in FIG. 4, the light-emitting display device 100 of this embodiment has a color filter 10 and a light-emitting body 80. There may be an inorganic oxide film 60 between the color filter 10 and the luminous body 80.

As a method of stacking the luminous body 80, for example, a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of the color filter can be cited , Or a method of attaching the luminous body 80 formed on another substrate to the inorganic oxide film 60, etc. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, the cathode 76, and other components of the light-emitting body 80 can use known ones as appropriate. The light-emitting display device 100 fabricated in this way can be applied to, for example, an organic EL display in a passive driving mode, as well as an organic EL display in an active driving mode.

Furthermore, the light-emitting display device of this embodiment is not limited to the light-emitting display device having the configuration shown in FIG. 4, and may be a commonly known configuration as a light-emitting display device using color filters.

[Example]

Hereinafter, the present invention will be specifically explained with reference to examples. The present invention is not limited by these records.

(Synthesis example 1: Synthesis of fluorine-containing monomer A)

Load 25 parts by mass of methacrylic acid, 2-(perfluorohexyl) ethyl vinyl ether (product name: CHEMINOX FAVE-6, manufactured by UNIMATEC) into a reactor equipped with a condenser, an air inlet for nitrogen, and a stirrer. 101 parts by mass The reaction was carried out at 60°C for 9 hours under a nitrogen atmosphere. After cooling, an aqueous potassium carbonate solution was added for neutralization. The obtained reaction liquid was washed with water and separated, the solvent was distilled off, and unreacted components were removed by drying under reduced pressure, thereby obtaining a fluoromonomer A.

(Synthesis example 2: Synthesis of fluorine-containing monomer B)

A reactor equipped with a condenser, an air inlet for nitrogen gas, and a stirrer was charged with 25 parts by mass of 2-hydroxyethyl methacrylate, 2-(perfluorohexyl) ethyl vinyl ether (product name: CHEMINOX FAVE-6, UNIMATEC (manufactured by UNIMATEC) 101 parts by mass, 2.0 parts by mass of trifluoroacetic acid, tetrahydrofuran 200 parts by mass, reacted at 60°C for 9 hours in a nitrogen atmosphere. After cooling, an aqueous potassium carbonate solution was added for neutralization. The obtained reaction liquid was washed with water and separated, the solvent was distilled off, and unreacted components were removed by drying under reduced pressure, thereby obtaining a fluoromonomer B.

(Synthesis Example 3: Synthesis of Giant Monomer A)

Put 80.0 parts by mass of PGMEA in a reactor equipped with a condenser, a funnel for addition, an air inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and while stirring under a nitrogen stream, it is heated to a temperature of 90°C. 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 (azobisisobutyronitrile) was added dropwise over 1.5 hours, and the reaction was continued for 3 hours. Next, the nitrogen flow was stopped, the reaction solution was cooled to 80°C, and 8.74 parts by mass of 2-isocyanatoethyl methacrylate (product name: Karenz MOI, manufactured by Showa Denko), 0.125 parts by mass of dibutyltin dilaurate, and 0.125 parts by mass of methoxyphenol and 10.0 parts by mass of PGMEA were stirred for 3 hours to obtain a 50.0% by mass solution of macromonomer A. The obtained macromonomer A was confirmed by GPC (Gel Permeation Chromatography) under the conditions of the N-methylpyrrolidone/polystyrene standard with 0.01mol/L lithium bromide added, and the mass average molecular weight ( Mw) is 3720, the number average molecular weight (Mn) is 1737, and the molecular weight distribution (Mw/Mn) is 2.14.

(Synthesis Example 4: Synthesis of Fluoropolymer A)

Put 80.0 parts by mass of PGMEA in a reactor equipped with a condenser, an addition funnel, an air inlet for nitrogen, a mechanical stirrer, and a digital thermometer. While stirring under a nitrogen stream, the reactor is heated to a temperature of 75°C. The fluorine-containing monomer A of Synthesis Example 1 19.44 parts by mass, polybutylene oxide-based macromonomer (product name: Blemmer 10PPB-500B, manufactured by NOF), 40.56 parts by mass, PGMEA 56.0 parts by mass, and heat were added dropwise over 1.5 hours. A mixed solution of 1.2 parts by mass of polymerization initiator (product name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was heated and stirred for 3 hours, and 0.12 parts by mass of V-65 was added. The mixed solution of 4.0 parts by mass of PGMEA was further matured at the same temperature for 1 hour, thereby obtaining a fluoropolymer A containing the structure represented by the above general formula (1-2). Furthermore, PGMEA was added to adjust the solid content to 20% by mass.

(Synthesis example 5~7: Synthesis of fluoropolymer B~D)

In Synthesis Example 4, except that the polybutylene oxide-based macromonomer was changed to the polypropylene oxide-based macromonomer (product name: Blemmer PP-800, manufactured by NOF) and the polycaprolactone-based macromonomer, respectively (Product name: PLACCEL FM5, manufactured by Daicel), except for the macromonomer A of Synthesis Example 3 (effective solid content: 40.56 parts by mass), synthesized in the same manner as Synthesis Example 4 containing the above general formula (1-2) Fluoropolymers B~D of the indicated structure.

(Synthesis Example 8: Synthesis of Fluoropolymer E)

In Synthesis Example 4, except that the fluorine-containing monomer A of Synthesis Example 1 was changed to the fluorine-containing monomer B of Synthesis Example 2, it was synthesized in the same manner as in Synthesis Example 4 containing the formula (1-1). The structure of fluoropolymer E.

(Comparative Synthesis Example 1: Synthesis of Fluoropolymer F)

In Synthesis Example 4, except that the fluorine-containing monomer A of Synthesis Example 1 was changed to 2-(perfluorohexyl)ethyl methacrylate (product name: CHEMINOX FAMAC-6, manufactured by UNIMATEC), the same as Synthesis Example 4 The fluoropolymer F was synthesized in the same way.

(Comparative Synthesis Examples 2~4: Synthesis of Fluoropolymer G~I)

In Comparative Synthesis Example 1, except that the polybutylene oxide-based macromonomer was changed to the polypropylene oxide-based macromonomer (product name: Blemmer PP-800, manufactured by NOF), the polycaprolactone-based macromonomer was changed to Fluoropolymers G~I were synthesized in the same manner as in Comparative Synthesis Example 1, except for the body (product name: PLACCEL FM5, manufactured by Daicel) and the macromonomer A of Synthesis Example 3 (effective solid content: 40.56 parts by mass).

For fluoropolymers A~H, GPC is used to obtain the mass average molecular weight (Mw) and number average molecular weight under the conditions of the N-methylpyrrolidone/polystyrene standard with 0.01mol/L lithium bromide added. (Mn) and molecular weight distribution (Mw/Mn). The results are shown in Table 1.

By thermogravimetric reduction (TG) measurement and gas chromatography mass spectrometry (GCMS) measurement, it was confirmed that the fluorine-containing polymers A~E obtained in Synthesis Examples 4 to 8 contain fluorine at a temperature above 100°C and below 250°C Thermally decomposable fluoropolymer for zone separation. In addition, it was confirmed that the fluorine-containing polymer F~I obtained in Comparative Synthesis Examples 1 to 4 did not desorb the fluorine-containing group in the temperature range of 100°C or higher and 250°C or lower.

Furthermore, as a result of the GCMS measurement held at 230°C for 30 minutes, the thermal decomposition of 2-(perfluorohexyl)ethyl vinyl ether was detected from the fluoropolymers A to E obtained in Synthesis Examples 4 to 8 However, the thermal decomposition products of fluorine-containing groups have not been detected from the fluorine-containing polymers F~I of Comparative Synthesis Examples 1 to 4.

In addition, the measurement of the thermal weight loss uses DTG-60A manufactured by Shimadzu. The measurement temperature range is from room temperature to 320°C, and the temperature rise rate is 10°C/min. The GCMS measurement is performed under the following conditions.

<Measurement conditions>

GCMS device: manufactured by Agilent Technologies

HP-5973N/6890N

Thermal decomposition method: continuous heating type thermal decomposition method (PY-2020iD type)

Thermal extraction temperature: 230°C (30 minutes)

Note inlet temperature: 320℃

Column: 5% phenyl-95% dimethylsiloxane (UA-5) slightly polar

Inner diameter: 0.25μm length: 30m

Column temperature: 50℃×5min (maintain) -10℃/min (increasing temperature) -320℃×3min (maintain)

Ionization method: Electron impact ionization method (EI method)

Detector: Quadrupole type detector

(Synthesis Example 9: Synthesis of Color Material A) (1) Synthesis of Intermediate A-1

With reference to the manufacturing method of Intermediate 3 and Intermediate 4 described in International Publication No. 2012/144521, 15.9 g of the following Intermediate A-1 (yield 70%) was obtained.

It was confirmed from the following analysis results that the obtained compound is the target compound.

‧MS(ESI)(m/z): 511(+), 2 price

‧Elemental analysis value: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (78.06%, 7.75%, 7.69%)

[化13]

(2) Synthesis of pigment 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 prepare an intermediate A solution. Next, add 10.44g (3.05mmol) of nH2O _{phosphotungstic acid H 3} [PW ₁₂ O _{40 ]‧nH 2} O(n=30) (manufactured by Nippon Inorganic Chemical Industry) into 100ml of water and stir at 90°C to prepare phosphorus Tungstic acid aqueous solution. Mix the prepared aqueous solution of phosphotungstic acid with the previous intermediate A-1 solution at 90°C, filter the resulting precipitate, and wash it with water. The obtained filter cake was dried to obtain 13.25 g of the blue colorant (colorant A) of the triarylmethane-based basic dye represented by the following chemical formula A.

It was confirmed from the following analysis results that the obtained compound is the target compound.

‧MS(ESI)(m/z): 510(+), 2 price

‧Elemental analysis value: CHN measured value (41.55%, 5.34%, 4.32%); theoretical value (41.66%, 5.17%, 4.11%)

[化14]

(Synthesis Example 10: Synthesis of Color B) (1) Synthesis of Intermediate B-1

Make 1-iodonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) 15.2g (60mmol), 4,4'-methylenebis(2-methylcyclohexylamine) (manufactured by Tokyo Chemical Industry) 7.15g (30mmol), tertiary butyl Sodium oxide 8.07g (84mmol), 2-Dicyclohexylphosphino-2',6',-dimethoxybiphenyl made by Aldrich 0.09g (0.2mmol), Palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.021g (0.1 mmol) was dispersed in 30 mL of xylene and reacted at 130-135°C for 48 hours. After the reaction, it was cooled to room temperature and water was added for extraction. Then, it was dried and concentrated with magnesium sulfate, thereby obtaining 13.84 g (yield 94%) of the following intermediate B-1.

It was confirmed from the following analysis results that the obtained compound is the target compound.

‧MS(ESI)(m/z): 491(M+H), 2879(MH2-)

‧Elemental analysis value: CHN measured value (85.72%, 8.53%, 5.75%); theoretical value (85.66%, 8.63%, 5.71%)

[化15]

(2) Synthesis of Intermediate B-2

15.0 g (59.7 mmol) of 4,4'-dichlorobenzophenone manufactured by Wako Pure Chemical Industries, Ltd. (manufactured by Wako Pure Chemical Industries, Ltd.), 16.3 g (121 mmol) of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.), Sodium tributoxide 16.1g (168mmol), 2-dicyclohexylphosphino-2',4',6',-triisopropylbiphenyl (manufactured by Johnson Matthey) 2.86g (6.0mmol), palladium acetate ( 673 mg (3.0 mmol) of Wako Pure Chemical Industries, Ltd. was dispersed in 130 mL of xylene, and reacted at 100-105°C for 20 hours. After the completion of the reaction, it was cooled to room temperature and 200 ml of toluene and 200 ml of water were added for extraction. 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 of the following intermediate B-2 (yield 44%).

It was confirmed from the following analysis results that the obtained compound is the target compound.

‧MS(ESI)(m/z): 449(M+H)

‧Elemental analysis value: CHN measured value (82.90%, 7.33%, 6.22%); theoretical value (82.81%, 7.40%, 6.23%)

(3) Synthesis of Intermediate B-3

Mix 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, and stir at 45-50°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 45-50°C for 20 hours. After the completion of the reaction, 100 ml of chloroform and 100 ml of water were added to dissolve, 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%).

It was confirmed from the following analysis results that the obtained compound is the target compound.

‧MS(ESI)(m/z): 677(+), 2 price

‧Elemental analysis value: CHN measured value (81.81%, 7.31%, 5.85%); theoretical value (81.77%, 7.36%, 5.90%)

(4) Synthesis of pigment B

Dissolve 1.7 g (1.19 mmol) of the above intermediate B-3 in 170 mL of methanol, and add n-hydrated phosphotungstic acid H ₃ [PW ₁₂ O ₄₀ ]‧ nH ₂ O to a mixture of 40 mL of methanol and 40 mL of water (n=30) (manufactured by Nippon Inorganic Chemical Industry) 2.59 g (0.76 mmol), stirred for 1 hour. The precipitate was filtered and washed with water. The obtained precipitate was dried under reduced pressure to obtain 3.4 g (95% yield) of a blue colorant (colorant B) represented by the following chemical formula B.

It was confirmed from the following analysis results that the obtained compound is the target compound.

‧MS(MALDI)(m/z): 1355(M+), 2879(MH2-)

‧Elemental analysis value: CHN measured value (35.55%, 3.24%, 2.61%); theoretical value (35.61%, 3.20%, 2.57%)

(Synthesis Example 11: Synthesis of Color 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. Put 3.85 g of polychloroaluminum chloride ("trade name: TAKIBINE # 1500" made by Taki Chemical, Al ₂ (OH) ₅ Cl, 83.5 mass% alkalinity, 23.5 mass% as alumina component) into 200 ml of water. It is dissolved to prepare an aqueous solution of polyaluminum chloride. The prepared polyaluminum chloride aqueous solution was added dropwise to the above dye solution at 80°C for 15 minutes, and then stirred at 80°C for 1 hour. Filter the formed precipitate and wash it with water. The obtained filter cake was dried to obtain 6.30 g (yield 96.2%) of salt-forming color material (color material C) of purple rhodamine-based acid dye.

(Synthesis Example 12: Synthesis of Color D)

Add 5.0 g of Acid Red 289 to 500 ml of water and dissolve it at 80°C to prepare a dye solution. Add 4.99 g of Alucard 2HP Flake (manufactured by Lion Akzo, dimethyl distearyl ammonium chloride, 95.5% effective solid content) into 85 g of isopropanol to dissolve it to prepare dimethyl distearyl ammonium chloride Solution. The dye solution was cooled to 5°C in an ice bath, and the prepared dimethyl distearyl ammonium chloride solution was added dropwise to the above dye solution at 5°C for 25 minutes, and then stirred at 5°C for 1 hour. Filter the formed precipitate and wash it with water. The obtained filter cake was dried to obtain 9.07 g (yield 97%) of salt-forming colorant (colorant D) of purple rhodamine-based acid dye.

(Synthesis Example 13: Synthesis of Adhesive Resin A)

Put 120 parts by mass of PGMEA as a solvent in a reactor equipped with condenser, addition funnel, nitrogen gas inlet, mechanical stirrer, and digital thermometer. After heating to 90°C in a nitrogen atmosphere, add continuously for 1.5 hours Containing 32 parts by mass of methyl methacrylate, 22 parts by mass of cyclohexyl methacrylate, 24 parts by mass of methacrylic acid, 2.0 parts by mass of AIBN as an initiator, and 4.5 parts by mass of n-dodecyl mercaptan as a chain transfer agent A mixture of parts by mass.

Thereafter, the reaction was continued while maintaining the synthesis temperature, and 0.05 parts by mass of p-methoxyphenol as a polymerization inhibitor was added 2 hours after the completion of the dropping.

Next, while blowing in air, 22 parts by mass of glycidyl methacrylate was added. After the temperature was raised to 110°C, 0.2 parts by mass of triethylamine was added, and the addition reaction was carried out at 110°C for 15 hours to obtain a binder resin. A (45% by mass solid content).

The obtained adhesive resin A has a mass average molecular weight (Mw) of 8850, a number average molecular weight (Mn) of 4200, a molecular weight distribution (Mw/Mn) of 2.11, and an acid value of 78 mgKOH/g.

(Manufacturing Example 1: Preparation of Salt-type Block Polymer Dispersant A Solution)

Dissolve 60.74 parts by mass of PGMEA, a block copolymer containing tertiary amine groups (trade name: BYK-LPN6919, manufactured by BYK-Chemie) (amine value 120mgKOH/g, solid content 60% by weight) 35.64 mass parts in the reactor. Parts (effective solid content 21.38 parts by mass), add 3.62 parts by mass of PPA (0.5 molar equivalent relative to the tertiary amine group of the block copolymer), and stir at 40°C for 30 minutes, thereby preparing the salt block Polymer dispersant A solution (25% solid content).

(Production Example 2: Production of Color Dispersion Liquid A)

As a colorant, 13.00 parts by mass of Colorant A of Synthesis Example 9 were mixed, 18.20 parts by mass of Dispersant A solution of Manufacturing Example 1 (4.55 parts by mass of solid content), and 13.00 parts by mass of Binder Resin A of Synthesis Example 13 (solid content) were mixed. Ingredients 5.85 parts by mass), 55.80 parts by mass of PGMEA, pre-dispersed with 2mm zirconia beads for 1 hour with a paint shaker (manufactured by Asada Iron Works), and then formally dispersed with 0.1mm zirconia beads for 4 hours to obtain a pigment dispersion Liquid A.

(Production Example 3: Production of Colorant Dispersion Liquid B)

In Production Example 2, the color material dispersion liquid B was obtained in the same manner as in Production Example 2 except that the color material was changed to 13.00 parts by mass of the color material B of Synthesis Example 10.

(Production Example 4: Production of Colorant Dispersion Liquid C)

In Production Example 2, the color material dispersion liquid C was obtained in the same manner as in Production Example 2, except that the color material was 12.22 parts by mass of the color material A of Synthesis Example 9 and 0.78 parts by mass of the color material C of Synthesis Example 11.

(Production Example 5: Production of Color Dispersion Liquid D)

In Production Example 2, except that the color material was set 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, a color material dispersion D was obtained in the same manner as in Production Example 2. .

(Production Example 6: Production of Color Dispersion Liquid E)

In Production Example 2, a colorant dispersion liquid E was obtained in the same manner as in Production Example 2 except that the colorant was a phthalocyanine-based pigment (Pigment Blue 15:6) 13.0 parts by mass.

(Manufacturing Example 7: Preparation of Adhesive Composition A)

啉基丙烷-1-酮(商品名：Irgacure 907，BASF製造)6.00質量份、2,4二乙基-9-氧硫

(商品名：kayacure DETX-S，日本化藥製造)2.00質量份，藉此製備黏合劑組合物A(固形物成分40質量%)。 PGMEA 44.36 parts by mass, 28.44 parts by mass of the binder resin A (solid content 45% by mass) of Synthesis Example 13, 5-6 functional acrylate monomers (trade name: ARONIX M402, manufactured by Toagosei), 19.20 parts by mass, 2 -Methyl-1[4-(methylthio)phenyl]-2-

Alkylpropan-1-one (trade name: Irgacure 907, manufactured by BASF) 6.00 parts by mass, 2,4 diethyl-9-oxysulfur

(Trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.) 2.00 parts by mass, thereby preparing adhesive composition A (solid content 40% by mass).

(Production Example 8: Preparation of coating layer composition) (1) Synthesis of polyester amide acid

A four-necked flask with a stirrer was charged with 143.5 parts by mass of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 25.0 parts by mass of 1,4-butanediol, and 20.0 parts by mass of benzyl alcohol , 23.0 parts by mass of 3,3'-diaminodiphenyl sulfide, 493.0 parts by mass of methyl 3-methoxypropionate as a solvent, and heated at 130°C for 3 hours under a nitrogen atmosphere for polymerization to obtain poly A 30% by mass solution of esteric acid.

(2) Preparation of coating layer composition

Mix 16.0 parts by mass of the 30% by mass solution of the polyester amide acid, 9.5 parts by mass of epoxy resin (trade name: EHPE3150, manufactured by Daicel), 0.9 parts by mass of trimellitic anhydride, and 3-glycidoxypropyl trimethoxy Silane (trade name: KBM403, manufactured by Shin-Etsu Chemical) 0.6 parts by mass, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, BASF Manufacturing) 0.2 parts by mass, 108.8 parts by mass of methyl 3-methoxypropionate, and 0.05 parts by mass of fluorine-based surfactant (trade name: MEGAFAC F447, manufactured by DIC), thereby A composition for a coating layer (solid content 20% by mass) was prepared.

(Example 1) (1) Preparation of photosensitive coloring composition A

33.57 parts by mass of the colorant dispersion A obtained in Production Example 2, 25.23 parts by mass of the adhesive composition A obtained in Production Example 7, 40.65 parts by mass of PGMEA, and the fluoropolymer of Synthesis Example 4 as a leveling agent A 0.25 parts by mass (0.05 parts by mass of effective solid content) was filtered under pressure to obtain the photosensitive coloring composition A of Example 1.

(2) Production of colored hardened film

Using a spin coater, the photosensitive coloring composition A obtained in the above (1) was coated on a glass substrate (manufactured by Nippon Electric Glass, "OA-10G") with a thickness of 0.7 mm. After that, it was heated and dried on a hot plate at 80°C for 3 minutes. An ultra-high pressure mercury lamp was used to irradiate 40mJ/cm ² of ultraviolet rays to obtain a blue colored hardened film. The substrate on which the above-mentioned cured film is formed is subjected to a post-baking treatment in a clean oven at 230°C for 30 minutes. Make the chromaticity after hardening become y=0.082.

(3) Formation of coating layer

The coating layer composition prepared in Production Example 8 was coated on the colored cured film obtained in (2) above using a spin coater. After that, it was heated and dried on a hot plate at 80°C for 3 minutes, and then baked in a clean oven at 230°C for 30 minutes.

<Leveling Evaluation>

For the colored cured film obtained in (2) above, observe whether there is unevenness on the film surface with a microscope. The results are shown in Table 2.

○: No unevenness

×: There is unevenness

<Recoatability Evaluation>

The presence or absence of shrinkage when the composition for a coating layer was spin-coated in (3) above was visually confirmed. The results are shown in Table 2.

○: No shrinkage

×: Shrinkage

<Optical performance evaluation>

Using the "Microscopic Spectrophotometer OSP-SP200" manufactured by Olympus, the chromaticity (x, y) and brightness (Y) of the finally obtained colored film were measured. The chromaticity (x, y) and brightness (Y) of the colored film are shown in Table 2.

(Examples 2 to 5, Comparative Examples 1 to 4)

In Example 1 (1), except that the fluoropolymer A of Synthesis Example 4, which is used as a leveling agent, was replaced with fluoropolymer B to E of Synthesis Examples 5 to 8, and Comparative Synthesis Examples 1 to 4 Except for the fluoropolymer F~I, the photosensitive coloring compositions of Examples 2 to 5 and Comparative Examples 1 to 4 were produced in the same manner as in Example 1 (1), and performance evaluation was performed in the same manner as in Example 1. . The results are shown in Table 2.

(Comparative Example 5)

In Example 1 (1), except for not adding a leveling agent, a photosensitive coloring composition of Comparative Example 5 was produced in the same manner as in Example 1, and performance evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Examples 6-9)

Using the photosensitive coloring compositions of Comparative Examples 1 to 4, between the steps (2) and (3) of Example 1, UV irradiation using a low-pressure mercury lamp for 5 minutes was performed, except for this, in the same manner as Example 1 Implement performance evaluation. The results are shown in Table 2.

(Examples 6-8, Comparative Examples 10-14)

According to Table 2 and Table 3, the types of colorants and fluoropolymers were changed, and the photosensitive colored resin compositions of Examples 6 to 8 and Comparative Examples 10 to 14 were prepared. According to Tables 2 and 3, the presence or absence of ultraviolet radiation was changed. Implement performance evaluation. The results are shown in Tables 3 and 4. Furthermore, the color material column in Table 4 indicates the combination of color material and the content ratio (mass ratio) of the color material.

[Result summary]

The coloring layer of Comparative Example 5 that does not contain fluoropolymer has poor leveling properties and poor smoothness.

The colored layers of Comparative Examples 1 to 4 of fluoropolymers containing non-thermally decomposable fluoropolymers repelled the coating layer composition when the ultraviolet cleaning step was not carried out, and the recoatability was poor. On the other hand, by performing an ultraviolet cleaning step (Comparative Examples 6 to 9), the recoatability was improved, but compared with Examples 1 to 5, the brightness of the colored layer decreased.

It is clearly used as the coloring layer formed by the coloring composition of Examples 1 to 5 using a salt-forming colorant containing a dye and a thermally decomposable fluorine-containing polymer separated from a temperature range of 100°C or more and 250°C or less. It has excellent performance and recoatability without ultraviolet cleaning step, and it becomes a high-brightness coloring layer.

It is also clear from the comparison between Example 6 and Comparative Example 10, and the comparison between Examples 7-8 and Comparative Examples 11-14: The resin composition according to the present invention can form high brightness, has high smoothness, and is easy to The coloring layer of the covering layer is formed on the surface.

There is provided a color composition comprising (A) a color material, (B) a dispersant, (C) a binder component, (D) a fluorine-containing polymer and (E) a solvent, wherein the color material (A) contains a salt-forming color material of a dye, and the fluorine-containing polymer (D) contains a thermally-decomposable, fluorine-containing polymer that a fluorine-containing group desorbs at a temperature in a range of from 100°C to 250° C.

Claims (11)

A coloring composition containing (A) colorant, (B) dispersant, (C) binder component, (D) fluoropolymer, and (E) solvent. The above-mentioned (A) colorant contains the following general formula The color material represented by (I), the above (D) fluoropolymer contains fluorine-containing thermally decomposable fluoropolymer based on the temperature range above 100°C and below 250°C, the total content of the above (A) color material The total solid content of the coloring composition is 5-65% by mass, and the total content of the above-mentioned (B) dispersant is 1-60% by mass relative to the total solid content of the coloring composition. (C) Adhesive The total content of the agent components relative to the total solid content of the coloring composition is 5 to 90% by mass, and the total content of the above (D) fluoropolymer relative to the total solid content of the coloring composition is 0.01 to 1 mass% %, the total content of the above (E) solvent is 65-95% by mass relative to the total amount of the coloring composition,

(In the general formula (I), A is an organic group with a valence of a carbon atom directly bonded to N without a π bond. The organic group means that at least the terminal directly bonded to N has a saturated aliphatic hydrocarbon group and is in the carbon chain It may contain O, S, N aliphatic hydrocarbon groups, or the end directly bonded to N has aliphatic hydrocarbon groups and the carbon chain may contain O, S, N aromatic groups, R ⁱ , R ⁱⁱ , R ⁱⁱⁱ , R ^iv and R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may be bonded to form a ring structure, R ⁱⁱ ~ R ^v At least one is an aryl group, R ^vi and R ^vii each independently represent an optionally substituted alkyl group or an optionally substituted alkoxy group, Ar ⁱ represents an optionally substituted divalent aromatic group, and B ^c- represents C-valent anion, a and c represent integers of 2 or more, b and d represent integers of 1 or more, e represent 0 or 1, f and g represent integers of 0 to 4, f+e and g+e are 0 Above and below 4, there are a plurality of R ⁱ ~R ^vii , Ar ⁱ , e, f and g which may be the same or different). The coloring composition of claim 1, wherein the above-mentioned (D) fluorine-containing polymer is a side chain containing one or more structures selected from the following general formula (1-1) and the following general formula (1-2) The polymer;

(In general formula (1-1) and general formula (1-2), L ¹ represents an oxygen atom or a sulfur atom, R ¹ , R ² and R ³ each independently represent a hydrogen atom, and the number of carbon atoms that may have a substituent is 1 or more and 18 or less hydrocarbon groups, R _f represents an alkyl group having a fluorine atom or a polyalkylene ether group having a fluorine atom; R ¹ and R _f may be bonded to form a ring structure). A coloring composition containing (A) colorant, (B) dispersant, (C) binder component, (D) fluoropolymer, and (E) solvent. The above-mentioned (A) colorant contains the following general formula The colorant represented by (I), and the above-mentioned (D) fluorine-containing polymer is a structure having one or more selected from the following general formula (1-1) and the following general formula (1-2) in the side chain The polymer; the total content of the above (A) colorant relative to the total solid content of the coloring composition is 5-65% by mass, and the total content of the above (B) dispersant is relative to the total solid content of the coloring composition The amount is 1-60% by mass, the total content of the above (C) binder component is 5 to 90% by mass relative to the total solid content of the coloring composition, and the total content of the above (D) fluoropolymer is relative to the coloring The total solid content of the composition is 0.01-1% by mass, and the total content of the above-mentioned (E) solvent is 65-95% by mass relative to the total amount of the coloring composition.

(In general formula (1-1) and general formula (1-2), L ¹ represents an oxygen atom or a sulfur atom, R ¹ , R ² and R ³ each independently represent a hydrogen atom, and the number of carbon atoms that may have a substituent is 1 or more and 18 or less hydrocarbon groups, R _f represents an alkyl group having a fluorine atom or a polyalkylene ether group having a fluorine atom; R ¹ and R _f may be bonded to form a ring structure)

(In the general formula (I), A is an organic group with a valence of a carbon atom directly bonded to N without a π bond. The organic group means that at least the terminal directly bonded to N has a saturated aliphatic hydrocarbon group and is in the carbon chain It may contain O, S, N aliphatic hydrocarbon groups, or the end directly bonded to N has aliphatic hydrocarbon groups and the carbon chain may contain O, S, N aromatic groups, R ⁱ , R ⁱⁱ , R ⁱⁱⁱ , R ^iv and R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may be bonded to form a ring structure, R ⁱⁱ ~ R ^v At least one is an aryl group, R ^vi and R ^vii each independently represent an optionally substituted alkyl group or an optionally substituted alkoxy group, Ar ⁱ represents an optionally substituted divalent aromatic group, and B ^c- represents C-valent anion, a and c represent integers of 2 or more, b and d represent integers of 1 or more, e represent 0 or 1, f and g represent integers of 0 to 4, f+e and g+e are 0 Above and below 4, there are a plurality of R ⁱ ~R ^vii , Ar ⁱ , e, f and g which may be the same or different). The coloring composition of claim 1 or 3, wherein the (A) color material contains one or more selected from the group consisting of triarylmethane color materials and dibenzopyran color materials. The coloring composition of claim 1 or 3, wherein in the colorant represented by the above general formula (I), B ^c- is a heteropolyanion containing tungsten. A color filter is provided with a colored layer on a transparent substrate, and at least one of the colored layers is a cured product of the colored composition according to any one of claims 1 to 5. The color filter of claim 6, wherein a coating layer is further provided on the colored layer. A method for manufacturing a color filter, which is a method for manufacturing a color filter with a colored layer on a transparent substrate, and includes: step (i), forming any of claims 1 to 5 on the transparent substrate A coating film of a coloring composition; step (ii), which is to harden the above-mentioned coating film; and step (iii), which is to heat the hardened coating film. For example, the method for manufacturing a color filter of claim 8, which further has a step (iv) of forming a coating layer on the colored layer after the above step (iii), and the above step (iii) and the above step (iv) are There is no UV cleaning step in between. A liquid crystal display device comprising the color filter according to claim 6 or 7 above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. A light-emitting display device, which comprises the color filter of claim 6 or 7 and an organic light-emitting body.

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