JP2018024616A - Composition, cured film, color filter, method for producing color filter, liquid crystal display device, light emitting display device, and heat latent radical scavenger - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition having a smaller color difference before and after high-temperature heating, a cured film formed using the composition, a color filter formed using the composition, a liquid crystal display device and a light emitting display device having the color filter, and a novel heat latent radical scavenger that is deprotected by heating to function as a radical scavenger.SOLUTION: A composition contains (A) a compound represented by general formula (1), (B) a binder component, and (C) a solvent (Q is S or O; R1 and R2 independently represent a halogen atom, an alkyl group, an arylalkyl group, an acyl group, an alkoxy group, or an alkylthio group).SELECTED DRAWING: None

Description

  The present disclosure relates to a composition, a cured film, a color filter, a method for producing a color filter, a liquid crystal display device, a light-emitting display device, and a thermal latent radical scavenger.

In recent years, the market price of thin image display devices represented by displays and the like has become affordable year by year with the evolution of production technology, and the demand has increased and the production volume has increased. Reached the main stream. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, the amount of light is controlled by electrically driving the liquid crystal, and color expression is performed by the light passing through a color filter. Therefore, a color filter must be present in the color representation of a liquid crystal television and plays a major role in determining the performance of the display. In an organic light emitting display device, when a color filter is used for a white light emitting organic light emitting element, a color image is formed in the same manner as in a liquid crystal display device.

  As a recent trend, there is a demand for power saving of an image display device, and in order to improve the utilization efficiency of a backlight, an increase in luminance of a color filter is required. This is a big problem especially for mobile displays (cell phones, smartphones, tablet PCs).

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

  As one means for achieving high brightness, coloring compositions using dyes have been studied. Dyes generally have higher transmittance than pigments and can produce high-intensity color filters, but heat resistance and light resistance are poor, and chromaticity is likely to change during high-temperature heating in the color filter production process. There was a problem. In addition, the colored resin composition using a dye has a problem that the cured film has poor solvent resistance, and the dye is transferred to a cured film that does not contain a colorant such as an adjacent pixel or protective film of another color. . Furthermore, the coloring composition used by dissolving the dye is used for color filter applications such as the problem that foreign matters are likely to be deposited on the surface of the cured coating film during the drying process, and the contrast is significantly reduced by the fluorescence emission of the dye. There were many problems.

  As a technique for improving various resistances of dyes, a technique for salting dyes is known. However, even if a salt is formed in a dye, the conventional coloring composition fades the salt-forming colorant of the dye due to high-temperature heating performed during the formation of the colored layer, and the luminance of the colored layer actually decreases. It was still difficult to achieve high brightness.

  According to the present inventors, in Patent Document 1, a colored resin composition in which a lake pigment, a dispersant having a specific structure and an acidic organophosphorus compound, and a hindered phenol-based antioxidant are combined, It is disclosed that the coloring composition is excellent in heat resistance while using a lake pigment, suppresses fading of the colored layer due to high-temperature heating, and can form a high-luminance colored layer.

  In addition, for the formation of flattening films, protective films, spacers, interlayer insulating films, etc. for electronic components such as liquid crystal display devices, organic EL display devices, integrated circuit elements, solid-state image sensors, curable compounds and polymer compounds are used. A binder component is used. However, a binder component containing a curable compound, a polymer compound, or the like has a problem that a deterioration phenomenon such as yellowing may be observed when exposed to a high temperature during heat processing.

Patent Document 2 describes that a colorable composition containing a colorant and a latent antioxidant is excellent in sensitivity and heat resistance, and Patent Document 3 discloses a resin, a latent antioxidant, a polymerization initiator, and an unsaturated state. It is described that a radically polymerizable composition containing a monomer is excellent in sensitivity and heat resistance.
However, further improvements have been desired for the technology for suppressing the color difference before and after high-temperature heating.

JP 2014-1553569 A Japanese Patent Laying-Open No. 2015-131937 Japanese Patent Laying-Open No. 2015-163671

  The present disclosure relates to a composition in which a color difference before and after high-temperature heating is suppressed, a cured film formed using the composition, a color filter formed using the composition, a method for producing the color filter, and the color filter It is an object of the present invention to provide a liquid crystal display device and a light-emitting display device having a novel thermal latent radical scavenger which is deprotected by heating and functions as a radical scavenger.

  One embodiment of the present disclosure provides a composition comprising (A) a compound represented by the following general formula (1), (B) a binder component, and (C) a solvent.

(In General Formula (1), Q is a sulfur atom or an oxygen atom. R ¹ and R ² are each independently a halogen atom, an alkyl group, an arylalkyl group, an acyl group, an alkoxy group, or an alkylthio group. In addition, a plurality of R ¹ and R ² may each independently form a ring together with carbon atoms bonded to each other at adjacent substituents, and R ³ can be protected by heating. N and m are each independently an integer of 0 or more and 4 or less.)

In one embodiment of the present disclosure, R ^{3 in the} general formula (1) is at least one selected from the group consisting of monovalent groups represented by the following general formulas (2-1) to (2-6). A composition is provided that is a seed.

(In General Formula (2-1), R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, R ¹³ is a hydrocarbon group, and R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be bonded to each other to show a cyclic structure, and in general formula (2-2), R ¹⁴ is a hydrocarbon group, and in general formula (2-3), R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and in general formula (2-4), R ¹⁸ is a hydrocarbon group, in general formula (2-5), R ¹⁹ is an aromatic hydrocarbon group, and in formula (2-6), R ²⁰ is a hydrocarbon group, each of which may have a substituent, and an oxygen atom in the carbon chain. And sulfur atoms may be included.)

  One embodiment of the present disclosure provides a composition in which the color material (D) includes a salt-forming color material of a dye.

  One embodiment of the present disclosure provides a composition in which the color material (D) includes a salt-forming color material of a dye and a metal-containing ion.

  One embodiment of the present disclosure provides a composition in which the color material (D) includes a salt-forming color material of at least one of a triarylmethane dye and a xanthene dye and a metal-containing ion.

  One embodiment of the present disclosure provides a composition in which the color material (D) includes a color material represented by the following general formula (I).

(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to the nitrogen atom does not have a π bond, and the organic group is saturated at least at the terminal directly bonded to the nitrogen atom. It represents a family hydrocarbon aliphatic hydrocarbon group having a group, or an aromatic group having the aliphatic hydrocarbon group, an oxygen atom in the carbon chain, a sulfur atom, which may contain a nitrogen atom .B ^c- Represents a c-valent polyacid anion, R ^{i to} R ^v each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ⁱⁱ And R ⁱⁱⁱ , R ^iv and R ^v may be bonded to each other to represent a cyclic structure, Ar ¹ represents a divalent aromatic group which may have a substituent, and a plurality of R ^{i to} R ^v and Ar ¹ may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

  One embodiment of the present disclosure provides a composition in which the (B) binder component includes at least one of a radiation curable compound and a thermosetting compound.

  One embodiment of the present disclosure provides a cured film that is a cured product of the composition.

  One embodiment of the present disclosure provides a color filter including at least a transparent substrate and a colored layer on the transparent substrate, the color filter having a colored layer that is a cured product of any one of the compositions. To do.

  One embodiment of the present disclosure is a method of manufacturing a color filter including at least a transparent substrate and a colored layer on the transparent substrate, wherein at least one of the colored layers is replaced with any one of the compositions. Provided is a method for manufacturing a color filter, which has a step of forming using a color filter.

  One embodiment of the present disclosure provides a liquid crystal display device including the color filter, a counter substrate, and a liquid crystal layer positioned between the color filter and the counter substrate.

  One embodiment of the present disclosure provides a light-emitting display device including the color filter and a light emitter.

  One embodiment of the present disclosure provides a thermal latent radical scavenger represented by the following general formula (1).

(In General Formula (1), Q is a sulfur atom or an oxygen atom. R ¹ and R ² are each independently a halogen atom, an alkyl group, an arylalkyl group, an acyl group, an alkoxy group, or an alkylthio group. In addition, a plurality of R ¹ and R ² may each independently form a ring together with carbon atoms bonded to each other at adjacent substituents, and R ³ can be protected by heating. N and m are each independently an integer of 0 or more and 4 or less.)

  According to embodiments of the present disclosure, a composition in which a color difference before and after high-temperature heating is suppressed, a cured film formed using the composition, a color filter formed using the composition, and manufacture of the color filter It is possible to provide a method, a liquid crystal display device and a light-emitting display device having the color filter, and a novel thermal latent radical scavenger that is deprotected by heating and functions as a radical scavenger.

It is a schematic sectional drawing which shows an example of the color filter of this indication. It is a schematic sectional drawing which shows an example of the liquid crystal display device of this indication. It is a schematic sectional drawing which shows an example of the light emission display apparatus of this indication.

Hereinafter, embodiments and examples of the present disclosure will be described with reference to the drawings and the like. However, the present disclosure can be implemented in many different modes, and should not be construed as being limited to the description of the embodiments and examples illustrated below. In addition, the drawings may be schematically represented with respect to the width, thickness, shape, and the like of each part in comparison with actual aspects for clarity of explanation, but are merely examples, and the interpretation of the present disclosure may be interpreted. It is not limited. In addition, in the present specification and each drawing, elements similar to those described above with reference to the previous drawings are denoted by the same reference numerals, and detailed description may be omitted as appropriate. Further, for convenience of explanation, the description may be made using the terms “upper” or “lower”, but the vertical direction may be reversed.
In the present disclosure, when a certain configuration such as a certain member or a certain region is “above (or below)” another configuration such as another member or another region, unless otherwise limited, Includes not only when directly above (or directly below) another configuration, but also when above (or below) another configuration, i.e., another component in between (or below) another configuration Including the case where is included.

In the present disclosure, (meth) acryl represents each of acryl or methacryl, (meth) acrylate represents each of acrylate or methacrylate, and (meth) acryloyl group represents each of acryloyl group or methacryloyl group. Represents.
In the present disclosure, the terms “plate”, “sheet”, and “film” are not distinguished from each other based only on the difference in designation, and “film surface (plate surface, sheet surface)” is a target. When a film-like (plate-like, sheet-like) member is viewed as a whole and globally, it indicates a surface that coincides with the planar direction of the target film-like member (plate-like member, sheet-like member). .
In the present disclosure, the radiation includes electromagnetic waves (gamma rays, X-rays, ultraviolet rays, visible rays, infrared rays, microwaves, etc.) or particle rays (electron rays, α rays) having a function of generating chemical species that initiate necessary reactions. , Neutron beams, various atomic beams, etc.). Examples of radiation preferably used in the present invention include ultraviolet rays, visible rays, and electron beams.

1. Composition The composition of the present disclosure includes (A) a compound represented by the following general formula (1), (B) a binder component, and (C) a solvent.

(In General Formula (1), Q is a sulfur atom or an oxygen atom. R ¹ and R ² are each independently a halogen atom, an alkyl group, an arylalkyl group, an acyl group, an alkoxy group, or an alkylthio group. In addition, a plurality of R ¹ and R ² may each independently form a ring together with carbon atoms bonded to each other at adjacent substituents, and R ³ can be protected by heating. N and m are each independently an integer of 0 or more and 4 or less.)

Even if the composition of the present disclosure undergoes a high-temperature heating step, for example, a high-temperature heating step of 200 ° C. or higher after film formation, the composition of (A) contains the compound represented by the general formula (1). It is a composition capable of suppressing change. In addition, when the composition of the present disclosure further includes a color material, the color material includes (A) the compound represented by the general formula (1) even after a high-temperature heating step after film formation. It is a coloring composition which can also suppress fading and can suppress fading by high-temperature heating. Thus, the composition of the present disclosure can suppress color difference before and after high-temperature heating.
The reason why the composition of the present disclosure exhibits the effects as described above is estimated as follows.

(A) The compound represented by the general formula (1) contained in the composition of the present disclosure has a radical formed by elimination of the protecting group represented by R ³ under high-temperature heating after the coating film is formed. The function as a scavenger comes to be demonstrated. Normally, active oxygen increases under high-temperature heating, but (A) the deprotection body from which R ^{3 of the} compound represented by the general formula (1) is eliminated is subjected to high-temperature heating after film formation. It is presumed that peroxy radicals are captured at the initial stage of oxidation, and the highly active peroxy radicals are made to be somewhat stable hydroperoxides, thereby reducing the amount of peroxy radicals that promote the deterioration of the binder components and the fading of the coloring material. Moreover, (A) When the code | symbol Q of the compound represented by the said General formula (1) is a sulfur atom, it is estimated that a hydroperoxide is further decomposed | disassembled and chain start reaction is prevented. By these, in the composition of this indication, it is estimated that the yellowing of the binder component and fading of a coloring material by high temperature heating can be suppressed, and the color difference before and after high temperature heating can be suppressed.

The radical scavenger can inhibit a polymerization reaction due to radiation of the binder component during film formation or a curing reaction due to heat, and can particularly inhibit a curing reaction involving radicals.
On the other hand, the compound represented by the general formula (1) contained in the composition of the present disclosure is heated as a radical scavenger when the protecting group represented by R ³ is eliminated. It has a thermal potential that it does not function as a radical scavenger in a state where the protecting group is not eliminated. Therefore, the composition of the present disclosure performs a heating or curing reaction under conditions where the protective group is not eliminated during film formation, and prevents the curing reaction during film formation from being inhibited by a radical scavenger, and In a high-temperature heating process such as post-baking, (A) the protective group of the compound represented by the general formula (1) is eliminated, thereby functioning as a radical scavenger, and deterioration of the binder component and fading of the coloring material Can be suppressed. In addition, the composition of the present disclosure can be stored under the condition that the protecting group is not eliminated during storage, and (A) the compound represented by the general formula (1) can be obtained by heating during film formation. When the protective group is eliminated, it functions as a radical scavenger and can suppress deterioration of the binder component and fading of the coloring material.
From the above, the composition of the present disclosure is a composition having high sensitivity and suppressing color difference before and after high-temperature heating without adversely affecting the film formation, for example, in the case of a radiation curable composition. .

The composition of the present disclosure includes (A) a compound represented by the following general formula (1), (B) a binder component, and (C) a solvent, and contains other components as necessary. You may do it. Hereinafter, each component will be described in order.
[(A) Compound represented by General Formula (1)]

(Each symbol in the general formula (1) is as described above.)

Since the compound represented by the general formula (1) has the above structure, the protecting group represented by R ³ in the drying step or the heating step at room temperature or lower than a certain temperature such as less than 150 ° C. Does not desorb and is inactive as a radical scavenger, for example, a high temperature heating step of a certain temperature or higher, such as 150 ° C. or higher, or 150 ° C. or higher in the presence of an acid or base contained in the composition. In such a high-temperature heating step above a certain temperature, the deprotectable protecting group represented by R ³ is eliminated and becomes active as a radical scavenger. Thus, the compound represented by the general formula (1) functions as a heat latent radical scavenger.

In the compound represented by the general formula (1), Q is preferably a sulfur atom.
Examples of the halogen atom represented by R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In each of the alkyl group, arylalkyl group, acyl group, alkoxy group, or alkylthio group represented by R ¹ and R ² , the included alkyl moiety may be independently linear, branched, or cyclic. Further, it may be saturated or unsaturated, and may further have a substituent. Further, the aryl group in the arylalkyl group may further have a substituent.

Examples of the alkyl group represented by R ¹ and R ² include an alkyl group having 1 to 24 carbon atoms, further an alkyl group having 2 to 18 carbon atoms, and further, 4 or more carbon atoms. Examples include 12 or less alkyl groups.
Examples of the alkyl group represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, a bornyl group, and an isobornyl group. , Dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group, vinyl group, allyl group, propenyl group and the like.

Examples of the arylalkyl group represented by R ¹ and R ² include an arylalkyl group having 7 to 24 carbon atoms, an arylalkyl group having 7 to 18 carbon atoms, and a carbon atom. Examples thereof include arylalkyl groups having a number of 7 or more and 12 or less.
Examples of the arylalkyl group represented by R ¹ and R ² include a benzyl group, an α, α-dimethylbenzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group.

Examples of the acyl group, alkoxy group or alkylthio group represented by R ¹ and R ² include an acyl group having 1 to 12 carbon atoms, an alkoxy group or an alkylthio group, and an acyl group having 1 to 8 carbon atoms. , An alkoxy group or an alkylthio group, and further an acyl group having 1 to 6 carbon atoms, an alkoxy group or an alkylthio group.
Examples of the alkyl moiety in the acyl group, alkoxy group or alkylthio group represented by R ¹ and R ² are the same as those in the alkyl group.
When it has an alkylthio group as at least one of R ¹ and R ² , it is preferable from the viewpoint of improving the function of decomposing hydroperoxide and preventing the chain initiation reaction.

Examples of the substituent at the alkyl moiety include a halogen atom and an alkoxy group having 1 to 4 carbon atoms.
Examples of the substituent of the aryl group in the arylalkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms. be able to.
The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

Moreover, several R < ¹ > and R < ² > may form the ring together with the carbon atom currently couple | bonded with them by adjacent substituents each independently. Examples of the ring structure formed include an aromatic ring and an aliphatic ring. Examples of the ring structure formed together with benzene rings bonded to each other at adjacent substituents include naphthalene ring, anthracene ring, phenanthrene ring, indene ring, tetrahydronaphthalene ring and the like.

The position where R ¹ and R ² are substituted is not particularly limited. For example, it is preferable that at least one of the 1-position, 2-position, 3-position, 7-position, 8-position, or 9-position is substituted, and at least the 2-position, 3-position, 7-position, or 8-position A case where one or more of them are substituted is preferred.

The substituent represented by R ¹ and R ² is used for the purpose of use so that the deprotection body from which R ^{3 of the} compound represented by the general formula (1) is eliminated functions as a radical scavenger during the high-temperature heating step. In addition, the number of substituents and the type of substituent may be appropriately selected. The deprotection body from which R ^{3 of the} compound represented by the general formula (1) is eliminated exhibits a sufficient antioxidant function during high-temperature heating, and exhibits the effect of suppressing color difference before and after high-temperature heating of the composition of the present disclosure. From the viewpoint of obtaining sufficiently, the number of substituents and the type of substituents are appropriately selected so that the deprotected body from which R ^{3 of the} compound represented by the general formula (1) is eliminated does not decompose at the temperature of the high-temperature heating step. do it.
n and m are each independently preferably an integer of 0 or more and 3 or less, and preferably 1 or more when the temperature of the high temperature heating step is 190 ° C. or more.
When the temperature of the high-temperature heating step is 230 ° C. or higher, in order to increase the thermal decomposition temperature of the deprotection body, for example, it is preferable to have at least one substituent having 2 or more carbon atoms. It is preferable to have two substituents having a number of 6 or more. An arylalkyl group such as an α, α-dimethylbenzyl group is suitably used for increasing the thermal decomposition temperature of the deprotected body.

R ³ is a protecting group that can be deprotected by heating. Here, “deprotectable” means that there is a possibility of changing from —NR ³ to —NH. R ³ is not particularly limited as long as (A) the compound represented by the general formula (1) is a protecting group that can be deprotected in a temperature range that functions as a thermal latent radical scavenger. R ³ is a functional group that functions as a protecting group for the —NH group that can be deprotected by heating under conditions in which the ring structure of the compound represented by the general formula (1) is not decomposed. It can be appropriately selected and used according to the temperature of the heating step. Further, when used as a composition according to an embodiment of the present disclosure, it is not particularly limited as long as the effect of the composition is not impaired, and is used in combination for the purpose of improving solubility and compatibility. What is necessary is just to select suitably by the kind of binder component and another compound, and an application method.

R ³ can be selected from a silyl group, a silanol group, a phosphino group, a phosphinyl group, a phosphono group, or a monovalent group having a hydrocarbon skeleton.

R ³ is at least one selected from the group consisting of monovalent groups represented by the following general formulas (2-1) to (2-6) because it can be deprotected by heating. preferable.

(In General Formula (2-1), R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, R ¹³ is a hydrocarbon group, and R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be bonded to each other to show a cyclic structure, and in general formula (2-2), R ¹⁴ is a hydrocarbon group, and in general formula (2-3), R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and in general formula (2-4), R ¹⁸ is a hydrocarbon group, in general formula (2-5), R ¹⁹ is an aromatic hydrocarbon group, and in formula (2-6), R ²⁰ is a hydrocarbon group, each of which may have a substituent, and an oxygen atom in the carbon chain. And sulfur atoms may be included.)

  The monovalent group represented by the general formula (2-1) can be obtained by reaction with a vinyl ether compound as follows, for example, when the reaction with phenothiazine is exemplified.

(In the formula, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are the same as those in the general formula (2-1).)

When R ¹⁰ , R ¹¹ , R ¹² and R ¹³ in the general formula (2-1) are obtained by the above reaction, they are determined by the structure of the vinyl ether compound used. The monovalent group represented by the general formula (2-1) depends on the type of (A) binder component and other compounds used in combination with the compound represented by the general formula (1) and the application method. It may be appropriately selected and is not particularly limited.
R ¹⁰ , R ¹¹ and R ¹² are preferably hydrogen or a substituted or unsubstituted alkyl group, allyl group or aryl group. In particular, hydrogen is preferable because of easy availability of raw materials. Moreover, it is preferable that the substituent which has active hydrogen, such as a primary, secondary, tertiary amino group, and a hydroxyl group, is not included from the point of stability of a compound.

R ¹³ in the general formula (2-1) is a hydrocarbon group. The hydrocarbon group may contain an oxygen atom or a sulfur atom in the carbon chain, and such a hetero atom part may be incorporated into an aromatic ring to form a heterocyclic ring. , May have a substituent. Examples of R ¹³ include a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a linear, branched, or cyclic saturated or unsaturated halogenated alkyl group, or an aromatic such as phenyl or naphthyl. A group containing an ether bond in a straight chain or branched chain saturated or unsaturated hydrocarbon skeleton (for example, — (R—O) _j —R ′, wherein R and R ′ are substituted) Or unsubstituted saturated or unsaturated hydrocarbon, j is an integer greater than or equal to 1; -R "-(O-R"') _k , where R "and R"' are substituted or unsubstituted saturated or unsaturated carbon Hydrogen, k is an integer of 1 or more,-(O—R ″ ′) _k is bonded to a carbon different from the terminal of R ″; and the like), linear or branched saturated or unsaturated A group containing a thioether bond in the hydrocarbon skeleton, linear or branched saturated or unsaturated carbonization Originally cyano group, a silyl group, a nitro group, an acetyl group, a group containing a hetero atom or hetero atoms such as an acetoxy group various groups formed by substitution. Further, R ^{13 of the} monovalent group represented by the above formula (2-1) may be linked to R ¹⁰ or R ¹¹ to have a cyclic structure. R ^{13 is} also preferably free from a primary, secondary, tertiary amino group, or a substituent having an active hydrogen such as a hydroxyl group from the viewpoint of the stability of the compound.

The monovalent group represented by the general formula (2-1) is deprotected by heating, but the deprotection temperature is generally directly bonded to the oxygen atom of the ether bond of the vinyl ether compound in R ¹³ in the above formula. The carbon atom is a tertiary carbon atom (hereinafter sometimes simply referred to as “tertiary carbon”) <secondary carbon atom (hereinafter sometimes simply referred to as “secondary carbon”) <primary There is a tendency to increase in the order of substituents of carbon atoms (hereinafter sometimes simply referred to as “primary carbon”).
On the other hand, the reaction between the vinyl ether compound for protection and the N—H group is generally performed in the order of substituents in which carbon atoms bonded to oxygen atoms are primary carbon <secondary carbon <tertiary carbon in R ¹³ in the above formula. Tends to show a high reaction rate.
Therefore, it is preferable to select a protective group as appropriate according to the temperature at which the composition is heated at a high temperature.
In the present disclosure, a carbon atom bonded to ether oxygen (a carbon atom bonded to an oxygen atom in R ¹³ of the general formula (2-1)) or a monovalent group of the general formula (2-1) With respect to the other carbon atom bonded to the ether oxygen bonded to the vinyl group of the vinyl ether compound to be derived, the primary carbon atom refers to the case where the other carbon atom bonded is 0 or 1. The secondary carbon atom refers to the case where there are two other carbon atoms bonded, and the tertiary carbon atom refers to the case where there are three other carbon atoms bonded.

R ¹³ in the general formula (2-1) preferably has 1 to 18 carbon atoms from the viewpoint of the volatility of the decomposition product, and more preferably 3 to 10 carbon atoms. .

Although it does not specifically limit as R < ¹³ > of General formula (2-1), For example, a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl Group, cyclohexylmethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, cyclohexyloxypropyl group, 2- Tetrahydropyranyl group etc. are mentioned. In the general formula (2-1), R ¹³ is linked to R ¹⁰ or R ¹¹ to form a cyclic structure, and the substituent corresponding to R ³ is a cyclic ether such as a 2-tetrahydropyranyl group. Etc.

  The monovalent group represented by the general formula (2-2) can be obtained, for example, by reaction with a carbamate protecting group. Examples of the carbamate protecting group include tert-butoxycarbonyl group (Boc-), benzyloxycarbonyl group (Z-), 9-fluorenylmethoxycarbonyl (Fmoc-), 1,1-dioxobenzo [b] thiophene- 2-ylmethoxycarbonyl group (Bsmoc-), 2- (4-nitrophenylsulfonyl) ethoxycarbonyl group (Nsc-), p-methoxybenzyloxycarbonyl group (Z (OMe-)), allyloxycarbonyl group (Alloc- ), 2,2,2-trichloroethoxycarbonyl group (Troc-) and the like.

Formula is not particularly limited as ^{R 14} in (2-2), for example, tert- butyl group, a benzyl group, 9-fluorenylmethyl group, 2,2,2-trichloroethyl, allyl, p- Examples include a methoxybenzyl group, 1,1-dioxobenzo [b] thiophen-2-ylmethyl group, 2- (4-nitrophenylsulfonyl) ethyl group, o-nitrobenzyl group and the like.

  The monovalent group represented by the general formula (2-3) can be obtained, for example, by reaction with a silyl protecting group. Examples of the silyl protecting group include trimethylsilyl group (TMS-), tert-butyldimethylsilyl group (TBDMS-), tert-butyldiphenylsilyl group (TBDPS-), triisopropylsilyl group (TIPS-), and the like.

Although it does not specifically limit as R < ¹⁵ >, R <^16> , R < ¹⁷ > of General formula (2-3), For example, alkyl groups, such as a methyl group, a tert- butyl group, an isopropyl group, and the aryl group of a phenyl group are used suitably. .

The monovalent group represented by the general formula (2-4) can be obtained, for example, by reaction with an acid chloride or an acid anhydride.
Examples of the acyl protecting group represented by the general formula (2-4) include an acetyl group (Ac-), a pivaloyl group, and a benzoyl group.

The R ¹⁸ in the general formula (2-4) is not particularly limited, for example, using an alkyl group such as methyl group and tert- butyl group, an aryl group such as a phenyl group, etc., preferably an arylalkyl group such as a benzyl group It is done.

The monovalent group represented by the general formula (2-5) can be obtained, for example, by reaction with a halide.
R ^{19 in the} general formula (2-5) is an aromatic ring which may have a substituent, and is not particularly limited, and examples thereof include a phenyl group and a naphthyl group which may have a substituent.

The monovalent group represented by the general formula (2-6) can be obtained, for example, by reaction with isocyanate. No particular limitation is imposed on the R ²⁰ in the general formula (2-6) include a benzyl group.

In the general formula (1), R ^{3 of the} compound represented by the general formula (1) needs to be deprotected during a high-temperature heating step for forming a layer used for a product such as a colored layer. The temperature at which R ³ of the represented compound is deprotected is set to a temperature lower than that of the high temperature heating step. As a guideline for the temperature at which R ^{3 of the} compound represented by the general formula (1) is deprotected, the 10% weight reduction temperature of the compound represented by the general formula (1) is, for example, 150 ° C. or more. Furthermore, 180 degreeC or more is mentioned. For example, 230 degrees C or less is mentioned, Furthermore, 200 degrees C or less is mentioned.

In addition, when the deprotected body from which R ^{3 of the} compound represented by the general formula (1) is eliminated does not exhibit an antioxidant function when decomposed during high-temperature heating, the composition of the present disclosure can be used before and after high-temperature heating. The color difference suppressing effect cannot be sufficiently obtained. Therefore, the 5% weight loss temperature of the deprotected body from which R ^{3 of the} compound represented by the general formula (1) is eliminated is preferably higher than the temperature of the high temperature heating step, and higher than the temperature of the high temperature heating step. It is preferably 15 ° C. or higher, preferably 50 ° C. or higher, and more preferably 70 ° C. or higher. The 5% weight reduction temperature of the deprotected product from which R ^{3 of the} compound represented by the general formula (1) is eliminated is, for example, preferably 190 ° C. or higher, more preferably 230 ° C. or higher, particularly preferably. Is 300 ° C. or higher. The 5% weight reduction temperature of the deprotected body can be appropriately adjusted by introducing the substituents represented by R ¹ and R ² .
In the present disclosure, the x% weight reduction temperature is the time when the weight of the sample is reduced by x% from the initial weight when the weight reduction is measured using a thermogravimetric analyzer (that is, the sample weight is the initial (100 -X) The temperature at the time of%).

  As a method for synthesizing the compound represented by the general formula (1), for example, a phenothiazine or phenoxazine is appropriately introduced by a conventionally known substituent introduction method, and then a conventionally known protective group introduction method is used. Or the method of introduce | transducing a protecting group into NH of phenoxazine or these derivatives is mentioned.

  The compound represented by the general formula (1) can be variously applied as a thermal latent radical scavenger. It is not limited to being used in combination with the binder component described below, and is suitably used for applications that are inactive at room temperature or low temperature and that become active during predetermined heating and function as a radical scavenger. It can also be used as a stopper or adhesive, or as a forming material for display devices, semiconductor devices, electronic components, micro electro mechanical systems (MEMS), stereolithography, optical members, or building materials. .

[(B) Binder component]
The composition of the present disclosure contains a binder component in order to impart film formability and adhesion to the surface to be coated. In order to impart sufficient hardness to the coating film, it is preferable to contain a curable binder component containing at least a curable compound. The curable binder component is not particularly limited. For example, for a colored layer of a color filter, a curable binder component used for forming a cured film for various known applications is appropriately selected according to the application. Can be used.
Examples of the curable binder component include a radiation curable binder component including a radiation curable compound that can be polymerized and cured by visible light, ultraviolet light, electron beam, and the like, and a thermosetting compound that can be polymerized and cured by heating. The thing containing the thermosetting binder component to contain can be used, These use the radiation curable binder component containing a conventionally well-known radiation curable compound and the thermosetting binder component containing a thermosetting compound suitably used. Can do.

In the case where the composition according to the present disclosure can be selectively deposited in a pattern on a substrate to form a cured film, for example, when used in an inkjet method, the curable binder component does not need developability. In this case, a known thermosetting binder component, a binder component, or the like that is used when a cured film is formed by an inkjet method or the like can be appropriately used. Moreover, also when forming the cured film which does not have a pattern shape, a well-known thermosetting binder component, a binder component, etc. can be used suitably.
As the thermosetting binder, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst capable of promoting a thermosetting reaction may be added. Examples of the thermosetting functional group include an epoxy group, an oxetanyl group, an isocyanate group, and an ethylenically unsaturated bond. An epoxy group is preferably used as the thermosetting functional group. Specific examples of the thermosetting binder component include those described in International Publication No. 2012/144521.

On the other hand, when using a photolithography process when forming a cured film, the radiation-curable binder component which has alkali developability is used suitably. In addition, you may further use a thermosetting binder component for a radiation-curable binder component.
Examples of the radiation curable binder component include a positive radiation curable binder component and a negative radiation curable binder component. Examples of the positive radiation curable binder component include a system containing an alkali-soluble resin and an o-quinonediazide group-containing compound as a radiation curable imparting component.

On the other hand, as the negative radiation curable binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a radiation initiator is preferably used.
In the composition according to the present disclosure, a negative radiation curable binder component is preferable because a pattern can be easily formed using an existing process by a photolithography method.
Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the radiation initiator that constitute the negative radiation-curable binder component will be specifically described.

(Alkali-soluble resin)
The alkali-soluble resin in the present disclosure has a carboxyl group, acts as a binder resin, and is appropriately selected and used as long as it is soluble in a developer used for forming a pattern, particularly preferably an alkali developer. be able to.
A preferable alkali-soluble resin in the present disclosure is a resin having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group and an epoxy (meth) acrylate resin having a carboxyl group. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a radiation polymerizable functional group such as an ethylenically unsaturated group in the side chain. It is because the film | membrane intensity | strength of the cured film formed by containing a radiation polymerizable functional group improves. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

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

Specific examples of the acrylic copolymer having a carboxyl group include those described in International Publication No. 2012/144521, specifically, for example, methyl (meth) acrylate, ethyl (meta )), Benzyl (meth) acrylate, cyclohexyl (meth) acrylate and other monomers having no carboxyl group, and (1) one or more copolymers selected from (meth) acrylic acid and anhydrides thereof. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer, a polymer or the like having an ethylenically unsaturated bond is polymerized with a polyfunctional monomer, which will be described later, upon irradiation with radiation. This is particularly suitable in that the cured film becomes more stable.

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

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

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

  Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, (meth) acryloyloxyethyl hexahydrophthalic acid, (Meth) acrylic acid dimer, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid and the like. These unsaturated group-containing monocarboxylic acids may be used alone or in combination of two or more.

Acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendo Dibasic acid anhydrides such as methylenetetrahydrophthalic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl Aromatic polycarboxylic acid anhydrides such as ether tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, endobicyclo- [2 , 2,1] -Hept-5-ene-2,3-dica Polycarboxylic anhydride derivatives such as carbon anhydride, and the like. These may be used alone or in combination of two or more.
The mass average molecular weight Mw of the epoxy (meth) acrylate compound having a carboxyl group thus obtained is not particularly limited, but is preferably 1000 or more and 40000 or less, more preferably 2000 or more and 5000 or less.

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

(Polyfunctional monomer)
The polyfunctional monomer used in the composition of the present disclosure is not particularly limited as long as it can be polymerized by a radiation initiator described later, and a compound having two or more ethylenically unsaturated double bonds is usually used. In particular, a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is preferable.
Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples include those described in International Publication No. 2012/144521.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, when the composition of the present disclosure requires excellent radiation curability (high sensitivity), the polyfunctional monomer has three (trifunctional) or more polymerizable double bonds. Preferred are poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol. Succinic acid modified products of tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate Dipentaerythritol hexa (medium ) Acrylate, and the like are preferable.
The content of the polyfunctional monomer used in the composition of the present disclosure is not particularly limited, but is usually about 5 parts by mass or more and 500 parts by mass or less, preferably 20 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. The range is 300 parts by mass or less. If the content of the polyfunctional monomer is less than the above range, the radiation curing does not proceed sufficiently and the irradiated part may be eluted, and if the content of the polyfunctional monomer is more than the above range, the alkali developability deteriorates. There is a fear.

(Radiation initiator)
There is no restriction | limiting in particular as a radiation initiator used in the composition of this indication, It can use combining 1 type (s) or 2 or more types from the conventionally well-known various radiation initiators. Specific examples include those described in International Publication No. 2012/144521.

  The content of the radiation initiator used in the composition of the present disclosure is usually 0.01 parts by mass or more and 100 parts by mass or less, preferably 5 parts by mass or more and 60 parts by mass with respect to 100 parts by mass of the polyfunctional monomer. It is as follows. If this content is less than the above range, the polymerization reaction cannot be sufficiently caused, so that the hardness of the cured film may not be sufficient. On the other hand, if it exceeds the above range, the solid content of the composition In some cases, the content of the coloring material or the like in the inside becomes relatively small, and a sufficient coloring density may not be obtained.

[(C) Solvent]
In the composition of the present disclosure, the solvent is not particularly limited as long as it is an organic solvent that does not react with each component in the composition and can dissolve or disperse them. Specifically, organic solvents such as alcohols, ether alcohols, esters, ketones, ether alcohol acetates, ethers, aprotic amides, lactones, unsaturated hydrocarbons, saturated hydrocarbons are used. Can be mentioned.
Among these, ether alcohols such as propylene glycol monomethyl ether; ether alcohol acetates such as methoxyethyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate, methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, propylene glycol monomethyl ether acetate; ethylene Ether systems such as glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and propylene glycol diethyl ether; ester systems such as 3-methoxybutyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate can be suitably used. .
Among them, as a solvent used in the present disclosure, MBA (3-methoxybutyl acetate), PGMEA (propylene glycol monomethyl ether acetate), DMDG (diethylene glycol dimethyl ether), diethylene glycol methyl ethyl ether, PGME (propylene glycol monomethyl ether) or these are used. What mixed is preferable from the point of the solubility of a dispersing agent, and application | coating suitability.

[Optional components]
The composition of the present disclosure may include various additives as necessary within a range where the effects of the composition are not impaired. Examples include the following, but are not limited thereto.

((D) Color material)
The composition of the present disclosure may contain (D) a color material used for forming a colored layer in advance.
The color material (D) used in the composition of the present disclosure is not particularly limited as long as it can produce a desired color. As the color material, for example, organic pigments, dyes, salt-forming color materials of dyes, and the like can be used alone or in admixture of two or more.
From the point of high transmittance and capable of producing a high-luminance color filter, the (D) coloring material in the composition of the present disclosure preferably contains a dye, but from the viewpoint of improving heat resistance and light resistance, It preferably contains a salt-forming colorant of a dye.

The salt forming color material of the dye may be a color material in which the dye forms a salt with a counter ion. Also included are organic pigments called lake pigments in which a water-soluble dye is precipitated with a rake agent (precipitating agent) to make it insoluble. Since the salt-coloring material of the dye is derived from the dye, it has a higher transmittance than a normal pigment and can form a high-luminance colored layer, but generally has a low heat resistance.
In the composition of the present disclosure, by containing the compound represented by the general formula (1), the amount of peroxy radicals in the film that promotes fading of the coloring material is reduced under high-temperature heating after film formation. Therefore, a salt-forming color material of a dye can be suitably used as the color material (D). When the composition of the present disclosure contains a salt forming color material of dye as the color material (D), the fading of the salt forming color material of the dye is suppressed even in a high-temperature heating step when the colored layer is formed. Therefore, it is possible to form a high-luminance colored layer using the salt-forming color material of the dye.
In the following description, when color index names are described, when only color index names having different numbers are listed, only the numbers may be listed.

  As the organic pigment, conventionally known organic pigments can be used, and are not particularly limited. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279; I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175 176,177,179,180,181,182,185,187,188,193,194,199,213,214; C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73; C. I. Pigment Green 7, 10, 36, 37, 58; I. The Cl substituents of Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. 80; C.I. I. Pigment violet 1, 19, 23, 27, 32, 37, 42; C.I. I. Pigment brown 25, 28; C.I. I. And CI pigment black 1 and 7.

A conventionally known dye can be used as the dye and is not particularly limited, and examples thereof include an acid dye, a basic dye, and a direct dye.
Specific examples of the acid dye include C.I. I. Acid Violet 15, 16, 17, 19, 21, 21, 24, 25, 38, 49, 72, C.I. I. Acid Blue 1, 3, 5, 7, 9, 19, 22, 83, 90, 93, 100, 103, 104, 109, C.I. I. Acid green 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 50, and the like triarylmethane acid dyes; I. Acid Red 50, 51, 52, 87, 91, 92, 93, 94, 98, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Acid Blue 19, C.I. I. Acid Orange 11, C.I. I. And xanthene acid dyes such as Acid Yellow 73 and 74 and Sulforhodamine 101. Among the xanthene acid dyes, C.I. I. Acid Red 50, C.I. I. Acid Red 52, C.I. I. Acid Red 289, C.I. I. Acid Violet 9, C.I. I. Acid Violet 30, C.I. I. A rhodamine acid dye such as Acid Blue 19 is preferred.

In addition, C.I. I. Acid Red 80, 81, 82, 83, C.I. I. Acid Violet 34, 36, 39, 41, 42, 43, 47, 48, 51, 63, 109, 126, C.I. I. Acid Blue 23, 25, 27, 35, 40, 41, 43, 45, 46, 47, 49, 51, 52, 53, 55, 56, 62, 68, 69, 78, 80, 81, 96, 111, 124, 127, 127: 1, 129, 138, 140, 145, 150, 175, 183, 215, 225, 230, 251, 258, 260, 264, 271, 277, 281, 290, 324, 344, 350, C. I. Anthraquinone acid dyes such as Acid Green 25, 27, 28, 36, 37, 38, 40, 41, 42, 44, 54, 95; I. Indigo acid dyes such as Acid Blue 74; C.I. I. Acid Blue 249, C.I. I. Phthalocyanine acid dyes such as Direct Blue 86 and 87; I. Acid Yellow 38, 42, 44, 56, 68, 79, 86, 87, 105, 117, 183, 219, 228, C.I. I. Acid Orange 4, 24, 25, 33, 45, 49, 55, 56, 63, 79, 95, 116, 128, 156, 165, C.I. I. Acid Red 47, 56, 65, 66, 70, 71, 73, 85, 86, 89, 97, 99, 104, 111, 112, 114, 115, 117, 119, 126, 128, 134, 142, 144, 145, 148, 150, 151, 154, 158, 163, 164, 170, 173, 323, 350, 351, 374, 444, C.I. I. Acid Violet 131, C.I. I. Acid Blue 26, 29, 36, 44, 85, 87, 92, 113, 114, 116, 118, 120, 128, 352, C.I. I. Acid Green 19, 20, 34, C.I. I. Direct yellow 4, 12, 13, 15, 24, 25, 31, 33, 34, 41, 42, 44, 50, 51, 52, 67, 69, 70, 72, 73, 74, 83, 86, 117, 118, 120, 130, 132, 134, 138, 142, 162, 167, C.I. I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 24, 25, 26, 29, 30, 31, 32, 33, 49, 69, 72, 74, 83, 85, 90, 92, 96, 101, 102, 104, 108, 118, C.I. I. Direct Red 2, 4, 6, 7, 8, 10, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 28, 29, 31, 33, 34, 36, 37, 39, 42, 43, 44, 46, 49, 50, 52, 53, 54, 55, 56, 57, 59, 60, 61, 62, 63, 67, 68, 72, 73, 74, 75, 77, 79, 81, 83, 85, 88, 89, 90, 98, 99, 101, 108, 110, 117, 120, 121, 122, 127, 130, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 173, 174, 176, 180, 181, 185, 186, 189, 191, 220, 224, 227, 239, 243, 250, 253, 257, 259, 260, 264, . I. Direct violet 1, 4, 5, 6, 7, 9, 11, 12, 13, 14, 16, 17, 21, 22, 25, 26, 27, 28, 31, 32, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 47, 48, 49, 51, 53, 57, 62, 63, 64, 66, 72, 77, 78, 79, 80, 81, 83, 85, 87, 88, 89, 102, 103, C.I. I. Direct Blue 1, 2, 3, 4, 6, 8, 9, 10, 11, 12, 14, 15, 16, 19, 21, 22, 23, 25, 26, 27, 29, 30, 31, 35, 36, 37, 38, 39, 42, 43, 45, 48, 49, 50, 51, 53, 54, 55, 58, 60, 63, 64, 65, 67, 76, 80, 84, 90, 93, 94, 95, 96, 98, 111, 116, 122, 123, 124, 128, 129, 130, 131, 132, 136, 138, 140, 145, 149, 150, 151, 152, 158, 164, 166, 167, 168, 175, 176, 177, 183, 184, 185, 191, 201, 214, 215, 218, 226, 230, 231, 273, 278, 290, 295, 297, 306, C I. Direct Green 1, 3, 6, 7, 8, 9, 10, 11, 12, 13, 19, 20, 21, 22, 34, 38, 39, 42, 49, 55, 57, 58, 60, 85, etc. Disazo acid dyes of
C. I. Acid Yellow 54, 59, 98, 99, 100, 106, 118, 120, 121, 151, 156, 220, 233, 241, 259, 260, 262, C.I. I. Acid Orange 61, 72, 74, 97, 125, 142, 148, 164, C.I. I. Acid Red 179, 180, 183, 184, 186, 187, 198, 201, 214, 251, 308, 357, 359, 362, 315, 316, 443, 405, 407, C.I. I. Acid Violet 56, 58, 61, 90, 91, 92, C.I. I. Acid Blue 42, 70, 154, 155, 158, 161, 169, 193, 198, 284, 317, 335, 349, C.I. I. Acid Green 12, 35, 43, 45, 73, 125, C.I. I. Monoazo acid dyes such as direct violet 46 and 56; and the like.

  The basic dye is an ionic dye having a cation moiety as a chromophore, such as diazine dyes, oxazine dyes, thiazine dyes, azo dyes, anthraquinone dyes, xanthene dyes, triarylmethane dyes. And dyes, phthalocyanine dyes, auramine dyes, acridine dyes, methine dyes, and the like. Specific examples include those with the following color index (CI) names.

Specific examples of basic dyes include C.I. I. Basic Red 2, 5, 6, 10, C.I. I. Basic Blue 13, 14, 16, C.I. I. Basic violet 5, 6, 8, 12, C.I. I. Diazine dyes such as basic yellow 14;
C. I. Oxazine dyes such as Basic Blue 3, 6, 10, 12, 74;
C. I. Basic Blue 9, 17, 24, 25, C.I. I. Thiazine dyes such as Basic Green 5;
C. I. Basic Red 18, 22, 23, 24, 29, 30, 31, 32, 34, 38, 39, 46, 51, 53, 54, 55, 62, 64, 76, 94, 111, 118, C.I. I. Basic Blue 41, 53, 54, 55, 64, 65, 66, 67, 162, C.I. I. Basic violet 18, 36, C.I. I. Basic Yellow 15, 19, 24, 25, 28, 29, 38, 39, 49, 51, 57, 62, 73, C.I. I. Azo dyes such as Basic Orange 1, 2, 24, 25, 29, 30, 33, 54, 69;
C. I. Anthraquinone dyes such as Basic Blue 22, 44, 47, 72;
C. I. Basic Red 1, 1: 1, 3, 4, 8, 11, C.I. I. Xanthene dyes such as basic violet 10, 11, 11: 1;
C. I. Basic Red 9, C.I. I. Basic Blue 1, 2, 5, 7, 8, 11, 15, 18, 20, 23, 26, 35, 81, C.I. I. Basic violet 1, 2, 3, 4, 14, 23, C.I. I. Triarylmethane dyes such as Basic Green 1 and 4;
C. I. Phthalocyanine dyes such as Basic Blue 140;
C. I. Auramine dyes such as basic yellow 2, 3, 37;
C. I. Basic Yellow 5, 6, 7, 9, C.I. I. Acridine dyes such as Basic Orange 4, 5, 14, 15, 16, 17, 18, 19, 23;
C. I. Basic Red 12, 13, 14, 15, 27, 28, 37, 52, 90, C.I. I. Basic Yellow 11, 13, 20, 21, 52, 53, C.I. I. Basic orange 21, 22, C.I. I. Examples thereof include methine dyes such as Basic Violet 7, 15, 16, 20, 21, and 22.
In the present disclosure, as the triarylmethane basic dye, a dye having a cation of a coloring material represented by the general formula (I) described later is also preferable.
These dyes can be used alone or in combination of two or more.

  In the salt coloring material of the dye, the counter ion varies depending on the kind of the dye, the counter ion of the acidic dye is a cation, and the counter ion of the basic dye is an anion. Therefore, the counter ion is appropriately selected and used according to the dye. That is, when the acid dye is insolubilized, a compound that generates a counter cation of the dye is used as a rake agent. When the basic dye is insolubilized, a counter anion of the dye is generated as a rake agent. A compound is used.

As counter cations of acid dyes, in addition to ammonium cations, metal cations such as phosphonium cations, sulfonium cations, calcium ions, barium ions, strontium ions, manganese ions, aluminum ions, cesium ions, lanthanum ions, neodymium ions, cerium ions, Examples thereof include inorganic polymers such as polyaluminum chloride and zirconium oxychloride.
Examples of the compound that generates ammonium ions include primary amine compounds, secondary amine compounds, tertiary amine compounds, and the like. Among them, secondary amine compounds are preferred because of their excellent heat resistance and light resistance. Alternatively, it is preferable to use a tertiary amine compound.

On the other hand, the counter anion of the basic dye may be an organic anion or an inorganic anion. Examples of the organic anion include organic compounds having an anionic group as a substituent. Examples of the anionic group include —SO ₂ N ^— SO ₂ CH ₃ , —SO ₂ N ^— COCH ₃ , —SO ₂ N ^— SO ₂ CF ₃ , —SO ₂ N ^— COCF ₃ , —CF ₂ SO _{2. ^{N - SO 2 CH 3, -CF}} 2 SO 2 N - COCH 3, -CF 2 SO 2 N - SO 2 CF 3, -CF 2 SO 2 N - COCF 3 or imidate group such as, -SO ₃ ^-, —CF ₂ SO ₃ ⁻ , —PO ₃ ²⁻ , —COO ⁻ , —CF ₂ PO ₃ ²⁻ , —CF ₂ COO ^{— and the} like can be mentioned. Among these, from the viewpoint of heat resistance and light resistance, an imido acid group, —SO ₃ ^— and —CF ₂ SO ₃ ^— are preferable, and —SO ₃ ^— (sulfonate group) is more preferable.
On the other hand, examples of the inorganic anion include an oxo acid anion (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ²⁻ ), molybdate ion (MoO ₄ ²⁻ ), and the like) Mention may be made of inorganic anions such as polyacid anions condensed with oxo acids and mixtures thereof.
The polyacid may be an isopolyacid anion (M _{m ′} O _{n ′} ) ^c- or a heteropolyacid anion (X _{l ′} M _{m ′} O _{n ′} ) ^c- . In the above ionic formula, M represents a poly atom, X represents a hetero atom, m ′ represents a composition ratio of poly atoms, n ′ represents a composition ratio of oxygen atoms, and l ′ represents a composition ratio of hetero atoms. Examples of the poly atom M include Mo, W, V, Ti, and Nb. Examples of the hetero atom X include Si, P, As, S, Fe, and Co. Moreover, a counter cation such as Na ⁺ or H ⁺ may be partially included.
Among these, an anion of an inorganic acid containing at least one of tungsten (W) and molybdenum (Mo) is preferable from the viewpoint of high brightness and excellent heat resistance and light resistance.

Examples of the polyacid containing at least one of tungsten (W) and molybdenum (Mo) include, for example, tungstate ion [W ₁₀ O ₃₂ ] ⁴⁻ and molybdate ion [Mo ₆ O ₁₉ ] ²⁻ which are isopolyacids. Or phosphotungstic acid ions [PW ₁₂ O ₄₀ ] ³⁻ , [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , silicotungstic acid ions [SiW ₁₂ O ₄₀ ] ⁴⁻ , phosphomolybdate ions [PMo] ₁₂ O ₄₀ ] ³⁻ , silicomolybdate ion [SiMo ₁₂ O ₄₀ ] ⁴⁻ , phosphotungsto molybdate ion [PW _12-x Mo _x O ₄₀ ] ³⁻ (x is an integer of 1 to 11), [P _{2 W 18-y Mo y O 62} ] 6- (y is 1 to 17 integer), Keita ring strike molybdate _{[SiW 12-x} o _x O _40] ^4- _(x is 1 to 11 integer), and the like. The polyacid containing at least one of tungsten (W) and molybdenum (Mo) is preferably a heteropolyacid among the above from the viewpoint of heat resistance and the availability of raw materials, and more preferably phosphorus (P It is more preferable that it is a heteropolyacid containing).
Furthermore, it is heat resistant to be any one of phosphotungsto molybdate ion [PW ₁₀ Mo ₂ O ₄₀ ] ³⁻ , [PW ₁₁ Mo ₁ O ₄₀ ] ³⁻ , and phosphotungstate ion [PW ₁₂ O ₄₀ ] ³⁻ . It is further preferable from the viewpoint of sex.

Examples of rake agents that generate inorganic anions include alkali salts and alkali metal salts of the above inorganic anions.
The counter ions in the salt forming colorant of the dye can be used alone or in combination of two or more.
Further, the counter ion in the salt forming color material of the dye preferably contains at least divalent ions from the viewpoint of improving various resistances.

  In the present disclosure, the salt-forming color material of the dye has a solubility of the color material at 23 ° C. of 0.1 (mg / 10 g solvent) or less with respect to the solvent contained in the composition from the viewpoint of improving various resistances. Further, the solubility of the coloring material at 23 ° C. is preferably 0.01 (mg / 10 g solvent) or less.

The solubility of the coloring material can be easily determined by the following evaluation method.
10 g of the solvent to be evaluated is put into a 20 mL sample tube bottle, and further 0.1 g of the coloring material is put in, covered, shaken well for 20 seconds, and then left to stand in a 23 ° C. water bath for 10 minutes. 5 g of this supernatant liquid is filtered to remove insoluble matters. The absorbance spectrum of a solution obtained by further diluting the obtained filtrate 1000 times is measured with a UV-visible spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation) using a 1 cm cell, and the absorbance at the maximum absorption wavelength is obtained. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solubility of the coloring material can be evaluated to be 0.1 (mg / 10 g solvent) or less.

  In addition, in the present disclosure, the salt forming color material of the dye is preferably a salt forming color material of a dye and a metal-containing ion from the viewpoint of heat resistance and light resistance. Among these, from the viewpoint of achieving high brightness, a salt-forming colorant comprising at least one of a triarylmethane dye and a xanthene dye and a metal-containing ion is preferable.

  In the present disclosure, the salt-forming color material of the dye and the metal-containing ion is particularly represented by the following general formula (I) from the viewpoint of excellent heat resistance and light resistance and achieving high brightness of the color filter. It is preferable to include a coloring material.

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

The cation part of the color material represented by the general formula (I) may be the same as the cation part of the color material represented by the general formula (I) described in International Publication No. 2012/144521.
A in the general formula (I) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) has no π bond, and the organic group is saturated at least at the terminal directly bonded to N. An aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group is represented, and O (oxygen atom), S (sulfur atom), and N (nitrogen atom) are present in the carbon chain. It may be included. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as the color tone and transmittance of the cationic coloring portion are not affected by the linking group A and other coloring portions, Similar colors can be retained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic unless the terminal carbon atom directly bonded to N has a π bond. The carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain contains O, S, and N. Also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
The aromatic group having an aliphatic hydrocarbon group in A is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N.
Especially, it is preferable that A contains a cyclic | annular aliphatic hydrocarbon group or an aromatic group from the point of the robustness of frame | skeleton.
Among the cyclic aliphatic hydrocarbon groups, a bridged alicyclic hydrocarbon group is preferable from the viewpoint of skeleton fastness. The bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridged structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane, dicyclopentadiene and adamantane. Among the bridged alicyclic hydrocarbon groups, norbornane is preferable. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Among these, the group containing a benzene ring is preferable.
From the viewpoint of easy availability of raw materials, A is preferably divalent to tetravalent, preferably divalent to trivalent, and more preferably divalent. For example, when A is a divalent organic group, an aromatic group in which two alkylene groups having 1 to 20 carbon atoms such as a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a xylylene group are substituted. Family groups and the like.

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

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

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

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

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

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

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

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

The anion (B ^c− ) of the colorant represented by the general formula (I) is a diacid or higher polyacid anion.
The polyacid anion may be appropriately selected from the polyacid anions as described above.
Among these, from the viewpoint of high brightness and excellent heat resistance and light resistance, it is preferably a polyacid anion containing at least one of tungsten (W) and molybdenum (Mo), including at least tungsten and containing molybdenum. It is more preferable that it is a good polyacid anion from the viewpoint of heat resistance.

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

The colorant represented by the general formula (I) may be a double salt containing other cations and anions as long as the effects of the present disclosure are not impaired. Specific examples of such cations include other basic dyes, organic compounds containing functional groups capable of forming salts with anions such as amino groups, pyridine groups, and imidazole groups, sodium ions, potassium ions, and magnesium ions. Metal ions such as calcium ion, copper ion and iron ion. Specific examples of anions include acid dyes, halide ions such as fluoride ions, chloride ions and bromide ions, and anions of inorganic acids. Examples of the anion of the inorganic acid include anions of oxo acids such as phosphate ions, sulfate ions, chromate ions, tungstate ions (WO ₄ ²⁻ ), and molybdate ions (MoO ₄ ²⁻ ).
In addition, as a coloring material represented by general formula (I), it can prepare with reference to international publication 2012/144520 pamphlet, for example.

The average dispersed particle size of the color material (D) used in the present disclosure is not particularly limited as long as it can produce a desired color when used as a colored layer of a color filter, and is excellent in dispersibility. From the viewpoint of improving contrast and brightness, and being excellent in heat resistance and light resistance, it is preferably in the range of 10 nm to 300 nm, and more preferably in the range of 20 nm to 200 nm. (D) When the average dispersed particle size of the color material is within the above range, the liquid crystal display device and the light emitting display device manufactured using the composition of the present disclosure may have high contrast and high quality. it can.
(D) The average dispersed particle diameter of the color material is a dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. For the measurement of particle size with a laser light scattering particle size distribution analyzer, the composition or the color material dispersion prepared in advance before preparing the composition is used in the solvent used in the composition. The concentration is appropriately diluted to a concentration measurable by (for example, 1000 times), and is measured by a dynamic light scattering method using a laser light scattering particle size distribution analyzer (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Microtrack Bell). It can be measured at ° C. The average dispersed particle size here is a volume average particle size.

  (D) The total content of the coloring material is preferably 3% by mass or more and 65% by mass or less, more preferably 10% by mass or more and 50% by mass or less, based on the total solid content of the composition. . If it is more than the said lower limit, the colored layer at the time of apply | coating a composition to predetermined | prescribed film thickness (usually 1.0 micrometer or more and 5.0 micrometers or less) has sufficient color density. Moreover, if it is below the said upper limit, while being excellent in the dispersibility and dispersion stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. In addition, in this indication, solid content is all things other than the solvent mentioned above, and a liquid polyfunctional monomer etc. are also contained.

(Dispersant)
The composition of the present disclosure preferably further includes a dispersant when (D) a coloring material is included. (D) The color material is preferably used by being dispersed in a solvent (C) with a dispersant. By uniformly dispersing the color material in the form of particles, the color material is not aggregated during coating film formation, and heat resistance and light resistance can be improved even with a salt-forming color material of a dye.
The dispersant can be appropriately selected from those conventionally used as known dispersants. As specific examples of the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed. These dispersants may be used alone or in combination of two or more.

  Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes Long chain polyaminoamide phosphates; polyethylenimine derivatives (amides and their bases obtained by reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters); polyallylamine derivatives (polyallylamine and free carboxyls) Polyester, polyamide or ester-amide co-condensation with groups The reaction product obtained by reacting one or more compound selected from among the three compounds of (polyester amide)), and the like.

  Examples of such commercially available dispersants include Disperbyk-2000, 2001, BYK-LPN6919, 21116, 21324 (above, manufactured by Big Chemie Japan), Azisper PB821, 881 (manufactured by Ajinomoto Fine Techno) and the like. it can. Among these, BYK-LPN6919 and 21116 are preferable from the viewpoint of heat resistance, electrical reliability, and dispersibility.

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

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

(In the general formula (II), R ²¹ is a hydrogen atom or a methyl group, L is a direct bond or a divalent linking group, Z is a group represented by the following general formula (II-a), or a substituent Represents a nitrogen-containing heterocyclic group which may have a group and can form a salt.)

(In General Formula (II-a), R ²² and R ²³ each independently represent a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R ²² and R ²³ may be the same or different from each other. May be.)

In general formula (II), L is a direct bond or a bivalent coupling group. The direct bond means that Z is directly bonded to the carbon atom in the general formula (II) without a linking group.
Examples of the divalent linking group in L include an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH— group, a —COO— group, and an ether group having a carbon atom number of 1 to 10 (—R ^24). —OR ²⁵ —: R ²⁴ and R ²⁵ are each independently an alkylene group), combinations thereof, and the like.
Among these, from the viewpoint of dispersibility, L in the general formula (II) is preferably a divalent linking group containing a direct bond, a —CONH— group, or a —COO— group.

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

As the polymer having the structural unit represented by the general formula (II), among others, WO2011 / 108495, JP2013-054200A, JP2010-237608A, JP2011-75661A The block copolymer having the structure described in the above and the graft copolymer can improve the dispersibility and dispersion stability of the coloring material and the heat resistance of the composition, and can form a colored layer with high brightness and high contrast. preferable.
Moreover, BYK-LPN6919 etc. are mentioned as a commercial item of the polymer which has a structural unit represented by general formula (II).
(Salt forming agent)
In the composition of the present disclosure, a preferable dispersant is a weight in which at least a part of the nitrogen portion of the structural unit represented by the general formula (II) forms a salt (hereinafter sometimes referred to as salt modification). It is a coalescence.
As the salt forming agent, acidic organic phosphorus compounds, organic sulfonic acid compounds, quaternizing agents and the like described in WO2011 / 108495 and JP2013-054200A can be suitably used. In particular, when the salt forming agent is an acidic organic phosphorus compound, a colored layer with higher brightness can be formed even after a high temperature heating step in the color filter manufacturing step.

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

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

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

(Other additives)
Other additives may be appropriately selected and used according to the application of the composition, and are not particularly limited. Other additives include, for example, other antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, etc. Etc.
Specific examples of the surfactant and the plasticizer include those described in International Publication No. 2012/144521.

<Combination ratio of each component in the composition>
The content of the compound represented by (A) the general formula (1) is not particularly limited, but is usually 0.1% by mass or more in the total solid content of the composition from the viewpoint of the color difference suppressing effect during the high-temperature heating process. 0.0 mass% or less, preferably 0.2 mass% or more and 4.0 mass% or less, more preferably 0.25 mass% or more and 3.0 mass% or less.

The binder component (B) is appropriately adjusted in consideration of the blending ratio with other components within the range where the total amount thereof is 99.9% by mass or less based on the total solid content of the composition. It may be used.
For example, when (D) a coloring material is not included, it is preferably blended at a ratio of 60% by mass or more and 99.9% by mass or less, preferably 80% by mass or more and 94.0% by mass or less.
Moreover, when (D) a coloring material is included, it is preferable to mix | blend in the ratio of 35 to 94 mass%, Preferably it is 40 to 87 mass%.

  What is necessary is just to set suitably content of the said (C) solvent in the range which can form a colored layer accurately. Usually, it is preferably in the range of 65% by mass or more and 95% by mass or less, more preferably in the range of 75% by mass or more and 88% by mass or less, with respect to the total amount of the composition containing the solvent. . When the content of the solvent is within the above range, the coating property can be excellent.

  The content of the color material (D) is preferably 5% by mass or more and 65% by mass or less, more preferably 8% by mass or more and 55% by mass or less, based on the total solid content of the composition. If the amount of the coloring material is too small, the transmission density when the composition is applied to a predetermined film thickness (usually 1.0 μm or more and 5.0 μm or less) may be insufficient. If the amount of the coloring material is too large, the composition There is a risk that the properties as a coating film, such as adhesion to the substrate when coated and cured on the substrate, surface roughness of the cured film, coating film hardness, etc. will be insufficient, and the color in the composition Since the ratio of the amount of the dispersant used for dispersing the material is also increased, characteristics such as solvent resistance may be insufficient. In addition, in this indication, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also included.

  The content of the dispersant is not particularly limited as long as it can uniformly disperse the color material. For example, the content is 1% by mass or more and 60% by mass with respect to the total solid content of the composition. % Is preferably in the range of 5% by mass or less, and particularly preferably in the range of 5% by mass or more and 50% by mass or less. If the amount of the dispersant is too small, it may be difficult to uniformly disperse the coloring material, and if the amount of the dispersant is too large, the curability and developability may be deteriorated.

<Method for producing composition>
The method for producing the composition of the present disclosure contains (A) a compound represented by the general formula (1), (B) a binder component, (C) a solvent, and various additive components used as desired. Any method can be used as long as a uniform composition is obtained, and the method is not particularly limited. It can prepare by mixing using a well-known mixing means.
Further, as a method for preparing the composition in the case of containing a color material, for example, (1) (D) a color material dispersion containing a color material, a dispersant, and (C) a solvent, and (B) a binder component And (A) a method of mixing the compound represented by the general formula (1) and various additive components used as desired; (2) two or more kinds of (D) coloring materials, each with a dispersant (C ) Dispersed in a solvent or other (D) colorant is prepared by dissolving in (C) solvent without using a dispersant, and optionally a colorant solution, and (B) a binder component (A) A method of mixing the compound represented by the general formula (1) and various additive components used as desired; (3) (C) In a solvent, (D) a coloring material, a dispersant, (B) a binder component, (A) the compound represented by the general formula (1), and each used as desired (4) (C) In a solvent, a dispersant, (B) a binder component, (A) a compound represented by the general formula (1), and optionally, Examples thereof include (D) a method of adding and mixing a coloring material after adding and mixing various additive components to be used.
When the composition of the present disclosure includes (D) the color material in advance, the method of preparing the color material dispersion in the above (1) or (2) effectively prevents (D) aggregation of the color material. From the point that can be dispersed uniformly.

  The method for producing a color material dispersion includes (D) a color material, (C) a solvent, and a dispersant used as required, and (D) the color material is uniformly dispersed in the (C) solvent. Any method can be used, and it can be prepared by mixing using a known mixing means. Moreover, when using 2 or more types of (D) color materials, it is good also as a color material dispersion liquid of this indication by preparing a color material dispersion liquid separately about each color material, and mixing these.

  Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 mm or more and 2.00 mm or less, more preferably 0.10 mm or more and 1.0 mm or less.

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

The composition of the present disclosure is used in a process that undergoes a high-temperature heating process, and is suitably used for a wide range of applications in which the color difference is preferably suppressed before and after the high-temperature heating process. The composition of the present disclosure includes, for example, a paint, a printing ink, a sealant, or an adhesive, or a display device, a semiconductor device, an electronic component, a micro electro mechanical system (MEMS), and an optically shaped article. It is preferably used as a forming material for optical members or building materials.
Especially, the composition of this indication is used suitably as a composition for forming a colored layer, a protective film, a spacer, an interlayer insulation film, and an optical lens.

2. Cured film The cured film of the present disclosure is a cured product of the composition of the present disclosure.
The manufacturing method of the cured film of this indication is not specifically limited, What is necessary is just to select suitably according to the binder component contained in the said composition of this indication. In the composition of the present disclosure used for the cured film of the present disclosure, the binder component (B) includes at least one of a radiation curable compound and a thermosetting compound.
The method for producing a cured film of the present disclosure includes:
Applying the composition of the present disclosure onto a support;
Removing the solvent from the applied composition;
A step of irradiating the composition from which the solvent has been removed, or a step of curing by heating;
And a step of heating at a temperature at which the protecting group R ³ in the compound represented by the general formula (1) is eliminated.

When the step of curing by heating is included, the step of curing by heating and the step of heating at a temperature at which the protecting group R ³ in the compound represented by the general formula (1) is eliminated are simultaneously performed in the same step. Although it may be performed, it is preferably performed in different steps at different temperatures. For example, after the step of curing by heating at a temperature at which the protecting group R ³ in the compound represented by the general formula (1) is not eliminated, the protecting group R ³ in the compound represented by the general formula (1). It is preferable to have a step of heating at a temperature at which desorption occurs.

Moreover, when a radiation-curable compound is contained in the binder component of the composition of the present disclosure and the composition is a radiation-curable composition, the composition of the present disclosure is suitably used for a method for producing a cured film having a pattern shape. .
In this case, the manufacturing method of the cured film of the present disclosure is:
Irradiating the composition from which the solvent has been removed in a pattern; and
Developing the radiation-irradiated composition with a developer;
It is preferable to further include a step of heating the composition having the developed pattern shape at a temperature at which the protective group R ³ in the compound represented by the general formula (1) is eliminated.

In the step of applying, the support may be appropriately selected according to the use of the cured film, and is not particularly limited.
The coating method is not particularly limited, and known coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, and a spin coating method can be used.

Examples of the method for removing the solvent from the applied composition (so-called wet coating film) include a heating method and a heating method under reduced pressure. As the heating means, a conventionally known heating means may be appropriately selected and used. For example, a hot plate or an oven can be used.
Heating in the solvent removal step is preferably performed at a temperature at which the protecting group R ³ in the compound represented by the general formula (1) is not eliminated. As for the heating conditions of a solvent removal process, about 1 minute or more and 60 minutes or less are mentioned, for example in the range of 70 degreeC or more and 130 degrees C or less.

When irradiating the composition from which the solvent has been removed, as a light source, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, EUV (Extreme Ultraviolet), An electron beam etc. can be used and should just be selected suitably according to the sclerosis | hardenability of a binder component.
As a method of irradiating the composition from which the solvent has been removed in a pattern, it can be selectively performed by irradiating through a mask having a predetermined pattern shape or drawing by direct irradiation of an electron beam not through the mask. The method of irradiating radiation is mentioned.
In the case of a negative radiation curable composition, the radiation irradiated part is cured, and in the case of a positive radiation curable composition, the radiation irradiated part is given solubility in a developer.

The step of curing the composition from which the solvent has been removed by heating may be performed simultaneously with the heating of the solvent removal step, and at a temperature at which the protecting group R ³ in the compound represented by the general formula (1) is not eliminated. Preferably, it is done. As for the heating conditions of the process hardened | cured by heating, about 5 minutes or more and 6 hours or less are mentioned at 30 degreeC or more and less than 150 degreeC, for example. On the other hand, the step of curing the composition from which the solvent has been removed by heating is performed simultaneously with the step of heating at a temperature at which the protecting group R ³ in the compound represented by the general formula (1) described later is eliminated. Also good.

In the case of having a step of irradiating a pattern with radiation and developing a radiation-irradiated composition with a developer, the developer may be appropriately selected according to the binder component. For example, when an alkali-soluble resin is contained in the binder component, an alkali developer is preferably used. For example, a 0.4% aqueous solution, a 0.5% aqueous solution, a 0.7% aqueous solution of tetramethylammonium hydroxide, .38% aqueous solution. A general method can be adopted as the developing method.
In the case of a negative radiation curable composition, a film having a desired pattern shape is obtained by dissolving and removing the non-irradiated portion. In the case of a positive type radiation curable composition, a film having a desired pattern shape is obtained by dissolving and removing a radiation irradiated portion.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like.

The step of heating at a temperature at which the protecting group R ³ in the compound represented by the general formula (1) is eliminated is appropriately selected depending on the kind of the protecting group R ³ in the compound represented by the general formula (1). What is necessary is just to set heating conditions. By performing a high-temperature heating process such as so-called post-irradiation heat treatment (post-baking), the coating film can be sufficiently cured, and for example, moisture used in the rinsing process can be removed and cured. The resistance and hardness of the film, and the adhesion to the support can be improved.
Examples of the heating conditions include a temperature of 150 ° C. or higher, and preferably from 180 ° C. to 250 ° C. for 5 minutes to 120 minutes from the viewpoint of decomposition of unnecessary compounds and electrical reliability. It is done. Further, the transmittance can be further improved by performing the heat treatment in a nitrogen atmosphere.

  Applications of the cured film of the present disclosure include a colored layer, a protective film, a spacer, an interlayer insulating film, an optical lens, a glass substitute substrate sealant, and the like. When the cured film of the present disclosure is a cured product of a composition containing (D) a color material, it is particularly suitable for a colored layer for a color filter, and (D) a cured product of a composition that does not contain a color material. In some cases, it is particularly suitable for overcoat layers and spacers.

3. Color filter The color filter according to the present disclosure is a color filter including at least a transparent substrate and a colored layer on the transparent substrate, and the colored layer is (A) a compound represented by the general formula (1) , (B) a binder component, (C) a solvent, and (D) a coloring material, or a cured product thereof.
Further, the method for producing a color filter of the present disclosure is a method for producing a color filter comprising at least a transparent substrate and a colored layer on the transparent substrate,
It has the process of forming at least 1 of the said colored layer using the composition of this indication, It is characterized by the above-mentioned.

  Such a color filter according to the present disclosure will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view illustrating an example of the color filter of the present disclosure. According to FIG. 1, the color filter 10 of the present disclosure includes a transparent substrate 1, a light shielding unit 2, and a colored layer 3.

(Colored layer)
At least one of the colored layers in the color filter of the present disclosure comprises (A) a compound represented by the general formula (1), (B) a binder component, (C) a solvent, and (D) a color material. About each component of (A)-(D) which is a hardened | cured material of the containing composition, since it is as above-mentioned, description here is abbreviate | omitted.

The colored layer is usually formed in an opening of a light shielding part on a transparent substrate, which will be described later, and is usually composed of three or more colored patterns.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the colored composition, but is usually preferably in the range of 1 μm to 5 μm.

The method for forming the colored layer is not particularly limited as long as the effect of the color filter of the present disclosure is not impaired, and a conventionally known method for forming a colored layer of a color filter can be appropriately used.
The step of forming at least one of the colored layers using the composition of the present disclosure includes a step of forming the composition of the present disclosure by curing, and includes the same steps as the method for producing the cured film. It is mentioned to have.

(Shading part)
The light shielding part in the color filter of the present disclosure is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light-shielding portion include those obtained by dispersing or dissolving a black pigment in a binder, and metal thin films such as chromium and chromium oxide. This metal thin film may be a laminate of a CrO _{x ′} film (x _′ is an arbitrary number) and two Cr films, and a CrO _{x ′} film (x _′ is a film having a reduced reflectance). Arbitrary number), CrN _{y ′} film (y _′ is an arbitrary number) and three layers of Cr film may be laminated.
When the light-shielding part is a material in which a black color material is dispersed or dissolved in a binder, the light-shielding part can be formed by any method that can pattern the light-shielding part. Examples thereof include a photolithography method, a printing method, and an ink jet method using a coloring composition for a light shielding part.

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

(Transparent substrate)
The transparent substrate in the color filter of the present disclosure is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, a transparent rigid material with no flexibility such as quartz glass, alkali-free glass, or synthetic quartz plate, or a transparent or flexible film such as a transparent film, an optical plate, or flexible glass. Examples include flexible materials.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this indication, the thing of about 50 micrometers or more and less than 1 mm can be used, for example.
The color filter of the present disclosure includes, for example, an overcoat layer, a transparent electrode layer, an alignment film for aligning a liquid crystal material, a columnar spacer, and the like in addition to the transparent substrate, the light shielding portion, and the colored layer. It may be what was done. The color filter of the present disclosure is not limited to the configuration exemplified above, and a known configuration generally used for a color filter can be appropriately selected and used.

4). Liquid Crystal Display Device A liquid crystal display device of the present disclosure includes the color filter according to the present disclosure described above, a counter substrate, and a liquid crystal layer positioned between the color filter and the counter substrate.
Such a liquid crystal display device of the present disclosure will be described with reference to the drawings. FIG. 2 is a schematic diagram illustrating an example of the liquid crystal display device of the present disclosure. As illustrated in FIG. 2, the liquid crystal display device 40 of the present disclosure includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 15. In FIG. 2, an example in which an alignment film 13a is formed on the colored layer 3 side of the color filter 10 and an alignment film 13b is formed on the counter substrate 20 side, and a liquid crystal layer 15 is formed between the two alignment films 13a and 13b. Shows about. Further, in FIG. 2, the liquid crystal display device 40 includes a polarizing plate 25 a disposed outside the color filter 10, a polarizing plate 25 b disposed outside the counter substrate 20, and the counter substrate 20 of the liquid crystal display device 40. The example which has the backlight 30 arrange | positioned outside the polarizing plate 25b arrange | positioned at the side is shown.
Note that the liquid crystal display device of the present disclosure is not limited to the configuration illustrated in FIG. 2, and may be a configuration generally known as a liquid crystal display device using a color filter.

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

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. In addition, the liquid crystal layer can be formed by overlapping the color filter and the counter substrate under reduced pressure and bonding them with a sealant. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

Moreover, as a backlight used for the liquid crystal display device of this indication, it can select and use suitably according to the use of a liquid crystal display device. As the backlight, for example, a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp), a backlight unit using a white LED or a white organic EL as a light source can be provided.
As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, UV LED, red light emitting phosphor, and green light emitting fluorescence And a white LED that obtains white light by color mixing by combining a body and a blue light emitting phosphor. As the phosphor, quantum dots may be used.
When the color filter of the present disclosure includes the color material represented by the general formula (I), the color filter includes a blue coloring layer having high luminance, that is, high transmittance. Also suitable for backlights with strong green and red intensities and relatively weak blue intensities, such as combinations of white LEDs that combine red and green and blue to obtain white light Used for.

5. Light Emitting Display Device A light emitting display device according to the present disclosure includes the color filter according to the present disclosure described above and a light emitter. Examples of the light emitting display device according to the present disclosure include an organic light emitting display device having an organic light emitter as the light emitter. The light emitter is not limited to an organic light emitter, and an inorganic light emitter can also be used as appropriate.
Such a light emitting display device of the present disclosure will be described with reference to the drawings. FIG. 3 is a schematic diagram illustrating an example of the light-emitting display device of the present disclosure. As illustrated in FIG. 3, the light emitting display device 100 of the present disclosure includes the color filter 10 and a light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the light emitter 80.

As a method of laminating the light emitter 80, for example, a method of sequentially forming the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 on the upper surface of the color filter. For example, a method of attaching the light emitter 80 formed on another substrate onto the inorganic oxide film 60 may be used. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the light emitter 80, known structures can be used as appropriate. The light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the light-emitting display device according to the present disclosure is not limited to the light-emitting display device having the configuration illustrated in FIG. 3, and can generally be configured as a light-emitting display device using a color filter. .

  Hereinafter, the embodiment of the present disclosure will be specifically described with reference to examples. The embodiments of the present disclosure are not limited by these descriptions.

(Synthesis Example 1: Synthesis of Compound 1)
1.74 g of 3,7-dicumylphenothiazine (manufactured by Seiko Chemical) and 2.62 g of di-t-butyl dicarbonate are added to 20 g of acetonitrile, 0.49 g of 4-dimethylaminopyridine is further added, and the mixture is heated to 55 ° C. Stir for hours. Thereafter, the mixture is cooled to 25 ° C., 20 g of pure water is added, and the precipitate is separated by decantation, dissolved in hot methanol at 50 ° C., cooled to 10 ° C. or lower, and the precipitated solid is separated by filtration. By washing with cold methanol, 1.8 g (yield 79%) of Compound 1 represented by the following chemical formula (A) was obtained. It was confirmed by ¹ H-NMR (AVANCE 400 MHz manufactured by BRUKER) (solvent: DMSO-d ₆ ) that the target product was synthesized.
Chemical shift ppm (multiplicity, number of protons): 7.41-7.43 (d, 2H), 7.20-7.27 (m, 10H), 7.11-7.16 (m, 4H), 1.62 (s, 12H), 1.41 (s, 9H)
Moreover, it measured using the thermogravimetric analyzer (Shimadzu Corporation DTG-60A, measurement conditions: About 6 mg of samples, a temperature increase rate shall be 10 degree-C / min and it measures from room temperature (23 degreeC)-600 degreeC in nitrogen atmosphere). The 10% weight reduction temperature of the compound 1 represented by the following chemical formula (A) was 225 ° C., and the 5% weight reduction temperature of 3,7-dicumylphenothiazine as a deprotection body was 330 ° C.

(Synthesis Example 2: Synthesis of Compound 2)
Add 1.04 g of 2-ethylthiophenothiazine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.75 g of di-t-butyl dicarbonate to 10 g of acetonitrile, add 0.49 g of 4-dimethylaminopyridine, and heat to 55 ° C. for 2 hours. Stir. Thereafter, the mixture was cooled to 25 ° C., 20 g of pure water was added, and the precipitate was collected by decantation. By column purification (developing solvent chloroform), 1.40 g (yield 97) of compound 2 represented by the following chemical formula (B) was obtained. %)Obtained. It was confirmed by ¹ H-NMR (AVANCE 400 MHz manufactured by BRUKER) (solvent: DMSO-d ₆ ) that the target product was synthesized.
Chemical shift ppm (multiplicity, number of protons): 7.54-7.57 (dd, 1H), 7.51 (d, 1H), 7.43-7.45 (dd, 1H), 7.35- 7.40 (m, 2H), 7.19-7.26 (m, 2H), 2.98-3.00 (q, 2H), 1.44 (s, 9H), 1.22-1. 26 (t, 3H)
Further, the 10% weight reduction temperature of the compound 2 represented by the following chemical formula (B) measured in the same manner as in Synthesis Example 1 is 200 ° C., and the 5% weight reduction temperature of 2-ethylthiophenothiazine as a deprotection body is It was 245 ° C.

(Comparative Synthesis Example 1: Synthesis of Comparative Compound 1)
Irganox 1035 (manufactured by BASF) 2.572 g and di-t-butyl dicarbonate 3.492 g were added to acetonitrile 20 g, and further 4-dimethylaminopyridine 0.49 g was added, heated to 55 ° C. and stirred for 2 hours. Thereafter, the mixture was cooled to 25 ° C., 20 g of pure water was added, and the precipitate was collected by decantation. By column purification (developing solvent chloroform), 2.8 g (yield) of Comparative Compound 1 represented by the following chemical formula (C) 94%). It was confirmed by ¹ H-NMR (AVANCE 400 MHz manufactured by BRUKER) (solvent: DMSO-d ₆ ) that the target product was synthesized.
Chemical shift ppm (multiplicity, number of protons): 7.13 (s, 4H), 4.13-4.16 (t, 4H), 2.75-2.83 (t, 4H), 2.64- 2.73 (t, 4H), 2.50-2.62 (t, 4H), 1.46 (s, 18H), 1.28 (s, 36H)
In addition, the 10% weight reduction temperature of Comparative Compound 1 represented by the following chemical formula (C) measured in the same manner as in Synthesis Example 1 is 205 ° C., and the 5% weight reduction temperature of Irganox 1035 as a deprotection body is 320 ° C. there were.

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

(2) Synthesis of Blue Color Material α 5.00 g (4.58 mmol) of the intermediate 1 was added to 300 ml of water and dissolved at 90 ° C. to obtain an intermediate 1 solution. Next, 10.44 g (3.05 mmol) of phosphotungstic acid · n hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O (n = 30) (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) was placed in 100 ml of water, and 90 ° C. To prepare an aqueous phosphotungstic acid solution. The aqueous phosphotungstic acid solution prepared in the intermediate 1 solution was mixed at 90 ° C., and the formed precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g of a blue color material α as a metal lake color material of a triarylmethane basic dye represented by the following chemical formula (IV).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 510 (+), divalent, elemental analysis value: CHN measured value (41.55%, 5.34%, 4.32%); theoretical value (41.66%) (5.17%, 4.11%)

(Preparation Example 2: Synthesis of binder resin A)
A reactor equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer was charged with 120 parts by weight of PGMEA (propylene glycol monomethyl ether acetate) as a solvent, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. After that, 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 (2,2′-azobisisobutyronitrile) as an initiator and a chain transfer agent A mixture containing 4.5 parts by mass of n-dodecyl mercaptan was continuously added dropwise over 1.5 hours.
Thereafter, the reaction was continued while maintaining the synthesis temperature, and as a polymerization inhibitor 2 hours after the completion of the dropping,
0.05 parts by mass of p-methoxyphenol was added.
Next, while blowing air, 22 parts by mass of glycidyl methacrylate was added, the temperature was raised to 110 ° C., 0.2 parts by mass of triethylamine was added, and an addition reaction was carried out at 110 ° C. for 15 hours. 45 mass% solid content) was obtained.
The obtained binder resin A had 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.

(Preparation Example 3: Preparation of salt type block polymer dispersant A solution)
35.64 parts by mass of PGMEA 60.74 parts by mass and a block copolymer containing a tertiary amino group (trade name: BYK-LPN6919, manufactured by Big Chemie) (amine value 120 mgKOH / g, solid content 60% by weight) (Effective solid content 21.38 parts by mass) were dissolved, and 3.62 parts by mass of PPA (phenylphosphonic acid) (0.5 molar equivalents with respect to the tertiary amino group of the block copolymer) were added. Was stirred for 30 minutes to prepare a salt type block polymer dispersant A solution (solid content 25%).

(Preparation Example 4: Production of Colorant Dispersion A)
As a colorant, 13.00 parts by mass of the blue colorant α of Preparation Example 1, 18.20 parts by mass of the salt-type block polymer dispersant A solution of Preparation Example 3 (solid content 4.55 parts by mass), and the binder of Preparation Example 2 Resin A 13.00 parts by mass (solid content 5.85 parts by mass) and PGMEA 55.80 parts by mass were mixed and pre-dispersed with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour with 2 mm zirconia beads, and further with 0 as main dispersion. Disperse with 1 mm zirconia beads for 4 hours to obtain a colorant dispersion A.

Example 1
(1) Preparation of binder composition A 44.36 parts by mass of PGMEA, 28.44 parts by mass of binder resin A (solid content 45% by mass) of Preparation Example 2, 5-6 functional acrylate monomer (trade name: Aronix M403, Toagosei Co., Ltd.) 14.40 parts by mass, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF) 6.00 parts by mass, 2, Binder composition A (solid content: 40% by mass) was prepared by mixing 2.00 parts by mass of 4 diethylthioxanthone (trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.).
(2) Preparation of composition 33.57 parts by mass of colorant dispersion A obtained in Preparation Example 4, 24.74 parts by mass of binder composition A obtained in (1) above, 40.94 parts by mass of PGMEA, synthesis Compound 1 obtained in Example 1 ((A) the compound represented by the general formula (1)) 0.20 part by mass (1.1% by mass with respect to the total solid content of the composition), surfactant R08MH ( 0.05 parts by mass of DIC) and 0.5 parts by mass of silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) were added and mixed, followed by pressure filtration to obtain the composition of Example 1. Compound 1 can function as a thermal latent radical scavenger in the composition.

(Example 2, Comparative Examples 1-4)
Example 2 was carried out in the same manner as Example 1 except that instead of Compound 1 in Example 1, (A) Compound 2 obtained in Synthesis Example 2 was used as the compound represented by Formula (1). A composition was obtained.
Further, in Example 1, instead of Compound 1, Example 1 except that the type and addition amount of the radical scavenger added to the binder composition were changed to the types and addition amounts as shown in Table 1. In the same manner, compositions of Comparative Examples 1 to 4 were obtained. However, when the radical scavenger was not added, the blending amount of the binder resin composition A was 25.23 parts by mass, and PGMEA was 40.65 parts by mass.
Further, 3,7-dicumylphenothiazine was manufactured by Seiko Chemical Co., and 2-ethylthiophenothiazine was manufactured by Tokyo Chemical Industry.

[Evaluation]
<Optical performance and heat resistance evaluation>
The composition obtained in each Example and Comparative Example was applied onto a glass substrate having a thickness of 0.7 mm (“OA-10G” manufactured by Nippon Electric Glass) using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (blue colored layer) was obtained by irradiating ultraviolet rays of 40 mJ / cm ² using an ultrahigh pressure mercury lamp. The chromaticity after curing is set to y = 0.082, and the chromaticity (x, y), luminance (Y), L, a, b (L ₀ , a ₀ , b ₀ ) of the obtained colored substrate Was measured using "Microspectrophotometer OSP-SP200" manufactured by Olympus. The substrate on which the colored film is formed is post-baked (PB) for 90 minutes in a clean oven at 230 ° C., and the chromaticity (x, y), luminance (Y), and L, a, b of the obtained colored film are obtained. (L ₁ , a ₁ , b ₁ ) and contrast were measured. Contrast was measured using “Contrast meter CT-1” manufactured by Osaka Co., Ltd.
As the heat resistance evaluation, the color difference (ΔEab) was calculated from the following formula.
ΔEab = {(L ₁ −L ₀ ) ² + (a ₁ −a ₀ ) ² + (b ₁ −b ₀ ) ² } ^1/2
Table 1 shows the chromaticity (x) and luminance (Y) of the colored film after post-baking, and the color difference (ΔEab) before and after post-baking.

<Developability evaluation>
The composition obtained in each Example and Comparative Example was applied on a glass substrate having a thickness of 0.7 mm (manufactured by Nippon Electric Glass, "OA-10G") using a spin coater, on a hot plate at 80 ° C. Was heated and dried for 3 minutes to form a blue colored layer having a thickness of 2.7 μm.
This colored layer was irradiated with ultraviolet rays of 40 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer was formed was subjected to shower development for 70 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. Among the independent thin lines of the obtained colored pattern substrate, the width (line width) of the actually measured independent thin line when the opening width of the photomask was 90 μm and the design line width was 110 μm was observed with a microscope.

(Summary of results)
In Examples 1 and 2 using the composition containing the compound represented by the general formula (1), the luminance (Y) after high-temperature heating is improved as compared with Comparative Example 1 in which no radical scavenger is added. Thus, it was revealed that the composition had a suppressed color difference (ΔEab) before and after high-temperature heating. Moreover, in Examples 1 and 2 using the composition containing the compound represented by the general formula (1), a line width similar to the designed line width is obtained after development, and a decrease in sensitivity to radiation is suppressed. A cured film was formed by curing.
In Examples 1 and 2 using the composition containing the compound represented by the general formula (1), the protecting group of the compound represented by the general formula (1) is not deprotected at the time of irradiation. Since it is inactive as a scavenger, a decrease in sensitivity to radiation is suppressed, and when heated at a high temperature of 230 ° C., the compound represented by the general formula (1) is released as a protecting group and becomes active as a radical scavenger. Therefore, it is considered that yellowing of the binder component and fading of the coloring material during high temperature heating were suppressed.
On the other hand, in Comparative Example 1 using a composition to which no radical scavenger was added, the sensitivity after the radical scavenger was not reduced, and a line width similar to the designed line width was obtained, but the brightness after high-temperature heating. The decrease in (Y) and the color difference (ΔEab) were large.
Moreover, in Comparative Examples 2 and 3 using a composition containing a phenothiazine-based radical scavenger that does not protect the NH group, the luminance after high-temperature heating is higher than that in Comparative Example 1 in which no radical scavenger is added. Although (Y) was improved and the color difference before and after high-temperature heating was suppressed, the line width was narrower than the designed line width. This is considered to be due to the fact that the radical scavenger exhibited radical scavenging ability during radiation irradiation and decreased sensitivity to radiation, and a cured film that was sufficiently cured could not be obtained.
Furthermore, in Comparative Example 4 using a hindered phenol-based radical scavenger protected with a protecting group, a line width similar to the designed line width was obtained after development, and a decrease in sensitivity to radiation was observed, It was clarified that the color difference equivalent to that of Comparative Example 1 in which a radical scavenger is not added is low in effect for suppressing the color difference during high-temperature heating.

  As described above, the composition of the present disclosure is a composition that suppresses yellowing of the binder component and fading of the coloring material during high-temperature heating without adverse effects during film formation, and suppresses the color difference before and after high-temperature heating. It was revealed that there was. In addition, since the latent radical scavenger of the present disclosure is deprotected by heating, it is possible to suppress a decrease in sensitivity to radiation compared to a normal radical scavenger and to form a sufficiently cured film. It was revealed.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored 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 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection Layer 73 hole transport layer 74 light emitting layer 75 electron injection layer 76 cathode 80 light emitter 100 light emitting display device

Claims (14)

(A) A composition comprising a compound represented by the following general formula (1), (B) a binder component, and (C) a solvent.
(In General Formula (1), Q is a sulfur atom or an oxygen atom. R ¹ and R ² are each independently a halogen atom, an alkyl group, an arylalkyl group, an acyl group, an alkoxy group, or an alkylthio group. In addition, a plurality of R ¹ and R ² may each independently form a ring together with carbon atoms bonded to each other at adjacent substituents, and R ³ can be protected by heating. N and m are each independently an integer of 0 or more and 4 or less.) R ^{3 in the} general formula (1) is at least one selected from the group consisting of monovalent groups represented by the following general formulas (2-1) to (2-6). The composition as described.
(In General Formula (2-1), R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, R ¹³ is a hydrocarbon group, and R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be bonded to each other to show a cyclic structure, and in general formula (2-2), R ¹⁴ is a hydrocarbon group, and in general formula (2-3), R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and in general formula (2-4), R ¹⁸ is a hydrocarbon group, in general formula (2-5), R ¹⁹ is an aromatic hydrocarbon group, and in formula (2-6), R ²⁰ is a hydrocarbon group, each of which may have a substituent, and an oxygen atom in the carbon chain. And sulfur atoms may be included.)   The composition which further contains (D) coloring material in the composition of Claim 1 or 2.   The composition according to claim 3, wherein the (D) coloring material includes a salt-forming coloring material of a dye.   The composition according to claim 3 or 4, wherein the color material (D) includes a salt-forming color material of a dye and a metal-containing ion.   The composition of any one of Claims 3-5 in which the said (D) coloring material contains the salt-forming coloring material of at least 1 of a triarylmethane type dye and a xanthene type dye, and a metal containing ion. The composition of any one of Claims 3-6 in which the said (D) coloring material contains the coloring material represented by the following general formula (I).
(In general formula (I), A is an a-valent organic group in which the carbon atom directly bonded to the nitrogen atom does not have a π bond, and the organic group is saturated at least at the terminal directly bonded to the nitrogen atom. It represents a family hydrocarbon aliphatic hydrocarbon group having a group, or an aromatic group having the aliphatic hydrocarbon group, an oxygen atom in the carbon chain, a sulfur atom, which may contain a nitrogen atom .B ^c- Represents a c-valent polyacid anion, R ^{i to} R ^v each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ⁱⁱ And R ⁱⁱⁱ , R ^iv and R ^v may be bonded to each other to represent a cyclic structure, Ar ¹ represents a divalent aromatic group which may have a substituent, and a plurality of R ^{i to} R ^v and Ar ¹ may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )   The composition of any one of Claims 1-7 in which the said (B) binder component contains at least 1 sort (s) of a radiation-curable compound and a thermosetting compound.   A cured film, which is a cured product of the composition according to claim 8.   A color filter comprising at least a transparent substrate and a colored layer on the transparent substrate, the color filter having a colored layer that is the composition according to any one of claims 3 to 8 or a cured product thereof. . A method for producing a color filter comprising at least a transparent substrate and a colored layer on the transparent substrate,
The manufacturing method of a color filter which has the process of forming at least 1 of the said colored layer using the composition of any one of Claims 3-8.   11. A liquid crystal display device comprising: the color filter according to claim 10; a counter substrate; and a liquid crystal layer positioned between the color filter and the counter substrate.   A light-emitting display device comprising the color filter according to claim 10 and a light emitter. A thermal latent radical scavenger represented by the following general formula (1).
(In General Formula (1), Q is a sulfur atom or an oxygen atom. R ¹ and R ² are each independently a halogen atom, an alkyl group, an arylalkyl group, an acyl group, an alkoxy group, or an alkylthio group. In addition, a plurality of R ¹ and R ² may each independently form a ring together with carbon atoms bonded to each other at adjacent substituents, and R ³ can be protected by heating. N and m are each independently an integer of 0 or more and 4 or less.)