KR20130083397A - Colorant, coloring composition, color filter and display device - Google Patents

Abstract

PURPOSE: A coloring composition is provided to produce a chromatic layer with the compatibility of high heat resistance and excellent voltage holding rate. CONSTITUTION: A coloring composition (A) comprises a coloring agent indicated as the following formula 1 (1)., a binder resin (B) and a cross-linking agent (C). In the following formula 1, X^+ is a cationic chromophore and Z^- is a conjugate base of an organic acid having a polymerizable unsaturated group and a halo group. The Z^- is an anion indicated as the following chemical formula (1a-1). In the following chemical formula (1a-1), Y^1 is a radical having a polymerizable unsaturated group and Y^2 is a halo group or a halide hydrocarbon group having a connecting group of atoms except carbon, hydrogen or halogen.

Description

COLORING COMPOSITION, COLOR FILTER AND DISPLAY DEVICE,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring composition, a color filter and a display device, and more particularly to a coloring composition, a color filter and a display device which are suitably used for a color filter such as a transmissive or reflective color liquid crystal display element, , A coloring composition containing the coloring agent, a color filter having a colored layer containing the coloring agent, and a display device having the color filter.

In the production of a color filter using a coloring and radiation-sensitive composition, a coloring and radiation-sensitive composition of a pigment dispersion type is coated on a substrate and dried, and then the dry film is irradiated with radiation in a desired pattern (hereinafter referred to as "exposure" (See Patent Documents 1 and 2) are known. Further, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. There is also known a method of obtaining pixels of respective colors by an ink jet method using a pigment dispersion type colored resin composition (Patent Document 4).

However, it is known that it is effective to use a dye as a coloring agent in order to realize high luminance and high color purity of a display element, or high definition of a solid-state image pickup element. For example, Patent Document 5 proposes the use of a triarylmethane dye having a specific structure.

Japanese Patent Application Laid-Open No. 2-144502 Japanese Patent Laid-Open Publication No. 3-53201 Japanese Patent Application Laid-Open No. 6-35188 Japanese Patent Application Laid-Open No. 2000-310706 Japanese Patent Application Laid-Open No. 2008-304766

However, the triarylmethane-based dye proposed in Patent Document 5 is insufficient in heat resistance, and if it is subjected to heating (post-baking) process after exposure and development exceeding 200 캜, the superiority of the chromaticity characteristic to the pigment is lost. Further, when a dye is used, a problem arises that the voltage holding ratio of the color filter deteriorates. From the above background, development of a coloring composition suitable for manufacturing a color filter capable of achieving both a high heat resistance and a good voltage holding ratio is strongly desired.

Accordingly, an object of the present invention is to provide a coloring composition suitable for forming a colored layer capable of achieving both a high heat resistance and a good voltage holding ratio. It is still another object of the present invention to provide a color filter comprising a colored layer formed from the colored composition and a display device including the color filter.

In view of such circumstances, the inventors of the present invention have conducted intensive studies and, as a result, have found that the above problems can be solved by using a colorant having an anion moiety as a conjugate base of an organic acid having a strong acidity and having an anionic polymerizable unsaturated group .

That is, the present invention provides a colored composition comprising (A) a colorant containing a compound represented by the following formula (1), (B) a binder resin and (C) a crosslinking agent.

[In the formula (1), X < ⁺ > represents a cationic chromophore;

Z ^- represents a conjugated base of an organic acid having a polymerizable unsaturated group and a halo group]

The present invention also provides a color filter comprising a colored layer containing a compound represented by the above formula (1) and a display element provided with the color filter. Here, the "colored layer" means each color pixel, a black matrix, a black spacer, etc. used in the color filter.

The present invention also provides a colorant represented by the above formula (1).

By using the coloring composition of the present invention, it is possible to form a colored layer that achieves both a high heat resistance and a good voltage holding ratio. Therefore, the coloring composition of the present invention can be suitably used for the production of various color filters including a color filter for a display element, a color filter for color separation of a solid-state image pickup element, a color filter for an organic EL display element, and a color filter for an electronic paper .

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the coloring composition of the present invention will be described in detail.

- (A) Colorant -

The coloring composition of the present invention contains (A) a coloring agent comprising a compound represented by the following formula (1) (hereinafter also referred to as "the present coloring agent").

[In the formula (1)

X < ⁺ > represents a cationic chromophore;

Z ^- represents a conjugated base of an organic acid having a polymerizable unsaturated group and a halo group]

First, Z ^- in the formula (1) will be described.

Z ^- is not particularly limited as long as it is a conjugate base of a polymerizable unsaturated group and an organic acid having a halo group. Acid is, for example, carboxylic acid (-CO ₂ H), sulfonic acid (-SO ₃ H), already deusan (-CONHCO-), sulfone imide acid (-SO ₂ NHSO ₂ -), oxo sulfamic acid ( -CONHSO ₂ -), and the like. In the present invention, among these acids, sulfonimidic acid (-SO ₂ NHSO ₂ -) and oxosulfamic acid (-CONHSO ₂ -) are preferable from the viewpoint of forming a conjugate base of an organic acid having a stronger acidity.

Suitable Z ^- groups in the present invention include, for example, an anion represented by the following formula (1a-1).

In the formula (1a-1)

Y ¹ represents a group having a polymerizable unsaturated group;

Y ² represents a halogen group or a halogenated hydrocarbon group which may have a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom]

Y ¹ is not particularly limited as long as it is a group having a polymerizable unsaturated group, but an organic group having a polymerizable unsaturated group is preferable. Examples of the organic group include chain organic groups and cyclic organic groups, with a chain organic group being preferred. The bonding position and bonding number of the polymerizable unsaturated group to these organic groups are arbitrary. In addition, when the organic group has a substituent other than the polymerizable unsaturated group, its kind, bonding position, and bonding number are not limited. Examples of the polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group, and an allyl group. In the present invention, since the anion has a polymerizable unsaturated group, the polymerizable unsaturated group causes a cross-linking reaction during exposure or post-baking, and the elution of the dye into the liquid crystal is inhibited. I guess.

Examples of particularly preferable Z ^- include anions represented by the following formulas (1a-2) and (1a-3).

In the formula (1a-2)

R ¹ represents a (meth) acryloyl group or an allyl group;

X ¹ represents -O- or -O- (R ² O) _q - (*) (wherein R ² represents an alkanediyl group having 2 or 3 carbon atoms, q represents an integer of 1 to 100, *) Represents the bonding hand with X ² );

X ² represents a substituted or unsubstituted alkanediyl group;

Y ² has agreed with the Y ² in the general formula (1a-1)] being

[In the formula (1a-3), R ³ represents a hydrogen atom or a methyl group;

X ³ represents a single bond or a substituted or unsubstituted alkanediyl group;

Y ² has agreed with the Y ² in the general formula (1a-1)] being

R ¹ represents a (meth) acryloyl group or an allyl group. From the ease of crosslinking reaction, a (meth) acryloyl group can be more preferably used.

R ² for X ¹ represents an alkanediyl group having 2 or 3 carbon atoms. Specific examples thereof include an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, Diethylene glycol and propane-1,2-diyl group are more preferable in terms of ease of production.

Q with respect to X ¹ is an integer of 1 to 100, preferably 1 to 30, more preferably 1 to 10, and particularly preferably 1 to 5.

As the alkanediyl group for X ² , an alkanediyl group having 1 to 10 carbon atoms is preferable. Specific examples include methylene, ethylene, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane- A butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,4-diyl group, a pentane-1,5-diyl group, A hexane-1,6-diyl group, an octane-1,8-diyl group, a decane-1,10-diyl group and the like. Of these, an alkanediyl group having 2 to 8 carbon atoms And an alkanediyl group having 2 to 6 carbon atoms is more preferable.

As the alkanediyl group for X ³ , an alkanediyl group having 1 to 10 carbon atoms is preferable. Specifically, the same groups as described above can be mentioned. Among them, an alkanediyl group having 1 to 8 carbon atoms is preferable, and an alkanediyl group having 2 to 6 carbon atoms is more preferable.

Representative examples of Y ¹ in the above formula (1a-1) include, for example, groups represented by the following formulas. In addition, "*" represents the bonding hand with N ^- .

Next, Y ² relating to the formula (1a-1), the formula (1a-2) and the formula (1a-3) will be described. Y ² represents a halogen group or a halogenated hydrocarbon group which may have a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom. Examples of the halo group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group include (1) an aliphatic hydrocarbon group, (2) an alicyclic hydrocarbon group, (3) an aliphatic hydrocarbon group having an alicyclic hydrocarbon group as a substituent (5) an aromatic hydrocarbon group having an aliphatic hydrocarbon group as a substituent (hereinafter referred to as an "aliphatic hydrocarbon-substituted aromatic hydrocarbon group"); (6) aromatic hydrocarbons (Hereinafter referred to as "aromatic hydrocarbon-substituted aliphatic hydrocarbon group"), and the like. The hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group is preferably the following characteristic group from the viewpoint of solubility in an organic solvent.

That is, the above-mentioned (1) aliphatic hydrocarbon group is preferably an alkyl group, and the alkyl group may be straight-chain or branched. The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 8 carbon atoms. The alicyclic hydrocarbon group (2) is preferably an alicyclic saturated hydrocarbon group, preferably 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon-substituted aliphatic hydrocarbon group (3) is preferably an alicyclic saturated hydrocarbon-substituted alkyl group, and the total carbon number thereof is preferably 4 to 20, and more preferably 6 to 14. The aromatic hydrocarbon group (4) is preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms (more preferably 6 to 10 carbon atoms), particularly preferably a phenyl group. The aliphatic hydrocarbon-substituted aromatic hydrocarbon group (5) is preferably an alkyl-substituted phenyl group, and the total carbon number thereof is preferably 7 to 30, more preferably 7 to 20. The aromatic hydrocarbon-substituted aliphatic hydrocarbon group (6) is preferably an aralkyl group, preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms. In this specification, the alkyl group may be linear or branched.

Among them, the hydrocarbon group constituting the skeleton of the halogenated hydrocarbon group is preferably an aliphatic hydrocarbon group, (3) alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, (4) aromatic hydrocarbon group, (5) aliphatic hydrocarbon-substituted aromatic hydrocarbon group or (6) an aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferable, and an alkyl group, an alicyclic saturated hydrocarbon-substituted alkyl group, a phenyl group, an alkyl-substituted phenyl group and an aralkyl group are more preferable, and an alkyl group is particularly preferable.

As the halogen in the halogen and halogenated hydrocarbon groups in Y ² , a fluorine atom is preferable from the viewpoint of the heat resistance of the colorant. By selecting a fluorine atom as a substituent, it is considered that the anion portion of the present colorant becomes a conjugate base of an organic acid having a stronger acidity than that of the present colorant, so that a salt having a stronger ion binding force is formed and heat resistance can be enhanced.

Examples of the connecting group containing an atom other than a carbon atom, a hydrogen atom and a halogen atom in Y ² include -O-, -S-, -CO-, -COO-, -CONH-, -SO ₂ - and the like . The carbon number in the paragraph [0051] means the total carbon number of the portion excluding the carbon atoms constituting the linking group.

In the present invention, Y ² is preferably a group represented by the following formula (1-1) or (1-2) in view of the heat resistance of the colorant, particularly preferably a group represented by the following formula ) Is preferable.

[In the formula (1-1)

R ²³ represents a hydrogen atom, a fluorine atom, an alkyl group, an alkyl fluoride group, an alicyclic hydrocarbon group, an alkoxy group, an alkoxy fluoride group, R ²⁴ COOR ²⁵ - or R ²⁴ COOR ²⁵ CFH- (R ²⁴ represents an alkyl group, an alicyclic hydrocarbon group, An aryl group, or a substituted or unsubstituted aryl group, and R ²⁵ represents an alkanediyl group;

n represents an integer of 0 or more;

"*" Indicates combined hands)

In the formula (1-2)

R ¹⁸ to R ²² independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkyl fluoride group or an alkoxy group;

"*" Represents a combined hand;

Provided that at least one of R ¹⁸ to R ²² is a fluorine atom or an alkyl fluoride group]

In the formula (1-1), R ²³ is preferably a fluorine atom, an alkyl fluoride group, an alicyclic hydrocarbon group, an alkoxy fluoride group, R ²⁴ COOR ²⁵ - or R ²⁴ COOR ²⁵ CFH-, A hydrocarbon group, a perfluoroalkoxy group, R ²⁴ COOCH ₂ CH ₂ - or R ²⁴ COOCH ₂ CH ₂ CFH-.

R ²⁴ represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group, or a substituted or unsubstituted aryl group. The alkyl group may be linear or branched, and the alkyl group has 1 to 12 carbon atoms (more preferably 1 to 8 carbon atoms) . The alicyclic hydrocarbon group may be a bridged alicyclic hydrocarbon group having 2 to 4 rings, and the number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 20 (more preferably 3 to 12). As the heteroaryl group, a group composed of a 5-10 membered aromatic heterocycle containing at least one hetero atom selected from a nitrogen atom, an oxygen atom and a sulfur atom is preferable. As the aryl group, an aryl group having 6 to 14 carbon atoms (more preferably 6 to 10 carbon atoms) is preferable, and a phenyl group is particularly preferable. The substituent includes, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a trifluoromethyl group, the position and the number of the substituent are arbitrary, , The substituents may be the same or different.

Further, R ²⁵ represents an alkanediyl group, and an alkanediyl group having 1 to 6 carbon atoms is preferable, and an ethylene group is particularly preferable in terms of ease of production.

The upper limit of n is preferably 10, more preferably 8.

In the formula (1-2), it is preferable that at least three of R ¹⁸ to R ²² are a fluorine atom or an alkyl fluoride group.

Specific examples of Y ² represented by the above formulas (1a-1), (1a-2) and (1a-3) include groups represented by the following formulas. Also, "*" represents a bond with SO ₂ .

Next, X ⁺ in the formula (1) will be described.

X ⁺ is a cationic chromophore, that is X ⁺ Z ^- as if the cation to form a basic coloring agent not particularly limited, and examples thereof include triarylmethane-based chromophores, methine-based chromophores, azo chromophore, diarylmethane-based chromophores, quinone An imine chromophore, an anthraquinone chromophore, a phthalocyanine chromophore, and a xanthan-based chromophore.

The triarylmethane chromophore is preferably represented by the following formula (2). Cations represented by the following formula (2) include various resonance structures, but in the present specification, they are equivalent to the cations represented by the following formula (2) for these resonance structures.

In the formula (2)

Ar represents a substituted or unsubstituted aromatic hydrocarbon group;

R ⁴ to R ⁷ independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a group having a phenyl group or an ethylenically unsaturated bond;

R ⁸ to R ¹⁵ represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, -COOR '(R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), or a halo group;

Y ³ represents a hydrogen atom or a group represented by the following formula (3)

[In the formula (3), R ¹⁶ and R ¹⁷ independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group or a group having an ethylenically unsaturated bond]

The aromatic hydrocarbon group in Ar is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms (more preferably 6 to 10 carbon atoms), specifically, a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group have. The substituent is, for example, an alkyl group having 1 to 6 carbon atoms, and the position and the number of the substituent are arbitrary. When two or more substituents are present, the substituents may be the same or different.

Examples of the alkyl group having 1 to 8 carbon atoms in R ⁴ to R ¹⁷ (including R 'in -COOR' in R ⁸ to R ¹⁷ ) include methyl, ethyl, propyl, isopropyl, Butyl, tert-butyl, isobutyl, amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, tertiary octyl, and 2-ethylhexyl.

Among the cations represented by the formula (2), in the present invention, from the viewpoint of improving the luminance and color purity, cations represented by the following formula (4) are particularly preferable.

[In formula (4), R ⁴ to R ⁷ and R ¹⁶ to R ¹⁷ are Im R ⁴ to R ⁷ and R ¹⁶ to R ¹⁷ and copper in the above formulas (2) and (3)]

In the above formula (4), R ⁴ , R ⁵ , R ¹⁶ and R ¹⁷ are preferably an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms), and R ⁶ is preferably an alkyl group having 1 to 8 carbon atoms more preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms), and preferably, R ⁷ roneun, still having 1 to 8 carbon atoms (more preferably an alkyl group or a hydrogen atom is preferred having 1 to 6 carbon atoms).

Representative examples of the cations represented by the above formula (2) include, for example, cations represented by the following formulas.

The methine chromophores are preferably represented by the following formulas (5-1) to (5-3).

[In the formulas (5-1) to (5-3)

R ³¹ represents a hydrogen atom or a halogen atom;

R ³² , R ³³ , R ³⁴ and R ³⁵ independently represent an alkyl group having 1 to 6 carbon atoms;

R ³⁶ represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms;

G is -CH = CH-, -CH = CH- NR 37 - (R 37 represents a hydrogen atom or an alkyl group having 1 to 6), -CH = N-NR 37 - (R 37 is synonymous with the Im) Or -N = N-NR ³⁷ - (R ³⁷ is the same as above);

R ^a represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group]

As R ^a , groups represented by the following formulas (5a) to (5g) are preferable.

In the formulas (5a) to (5g)

R ³⁸ and R ⁴⁵ independently represent an alkyl group having 1 to 6 carbon atoms;

R ³⁹ represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms;

R ⁴⁰ , R ⁴² , R ⁴³ and R ⁴⁴ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

R ⁴¹ and R ⁴⁶ independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group]

Examples of the substituent of the alkyl group include a halogen atom, a cyano group, and a hydroxyl group.

Representative examples of the cations represented by the above formulas (5-1) to (5-3) include, for example, cations represented by the following formulas.

The azo-based chromophore is preferably represented by the following formulas (6-1) to (6-6).

In the formulas (6-1) to (6-6)

R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁷ independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms;

R ⁵⁶ and R ⁶⁰ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group;

R ⁵⁸ represents an alkyl group having 1 to 6 carbon atoms;

R ⁵⁹ represents a group forming a quaternary ammonium;

R ^b represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group]

The R ⁵⁹ is preferably -NR ⁶¹ C _m H _2m N ⁺ R ⁶² R ⁶³ R ⁶⁴ (m is an integer of 1 to 5, R ⁶¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁶² and R ⁶³ And R ⁶⁴ independently represent an alkyl group having 1 to 6 carbon atoms, -COC _m H _2m N ⁺ R ⁶² R ⁶³ R ⁶⁴ (m, R ⁶² , R ⁶³ and R ⁶⁴ are the same as above), -C _m H _2m N ⁺ (NH ₂ ) R ⁷⁴ R ⁷⁵ wherein m is as defined above and R ⁷⁴ and R ⁷⁵ are independently of each other an alkyl group having 1 to 6 carbon atoms, 6-ii) is preferable.

[In the formulas (6-i) and (6-ii), R ⁶¹ and m are as defined above]

The R ^b is preferably a group represented by the following formulas (6a) to (6e), or a substituted or unsubstituted phenyl group.

[In the formulas (6a) to (6d)

R ⁶⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group;

R ⁶⁶ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms;

R ⁶⁷ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group;

R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

R ⁶⁹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

R ⁷⁰ to R ⁷³ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group]

Examples of the substituent of the alkyl group include a halogen atom, a hydroxyl group, a cyano group, and a -CONH ₂ group. Examples of the substituent of the phenyl group include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, and a nitro group.

Representative examples of the cations represented by the formulas (6-1) to (6-6) include, for example, cations represented by the following formulas.

The diarylmethane chromophore is preferably represented by the following formula (7-1) or (7-2).

[In the formulas (7-1) and (7-2)

R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ independently represent an alkyl group having 1 to 6 carbon atoms;

R ⁸⁵ , R ⁹⁰ and R ⁹¹ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]

Representative examples of the cations represented by the above formulas (7-1) to (7-2) include, for example, cations represented by the following formulas.

The quinone imine chromophore is preferably represented by the following formulas (8-1) to (8-3).

In the formulas (8-1) to (8-3)

R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ and R ¹¹⁸ independently represent a hydrogen atom , A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a benzyl group;

R ¹⁰⁷ and R ¹¹³ independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms;

R ¹¹² represents -NR ¹¹⁹ R ¹²⁰ (R ¹¹⁹ and R ¹²⁰ independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms), a hydroxyl group, a nitro group or a cyano group;

And Q represents an oxygen atom or a sulfur atom.

Examples of the substituent of the alkyl group include a halogen atom, a hydroxyl group, and a cyano group.

Representative examples of the cations represented by the formulas (8-1) to (8-3) include, for example, cations represented by the following formulas.

The anthraquinone-based chromophore is preferably represented by the following chemical formula (9-1) or (9-2).

[In the formulas (9-1) and (9-2)

R ¹³¹ , R ¹³⁵ and R ¹³⁶ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted phenyl group;

R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁸ , R ¹³⁹ and R ¹⁴⁰ independently represent an alkyl group having 1 to 6 carbon atoms;

R ¹³⁷ represents a methylene group or a substituted or unsubstituted alkanediyl group having 2 to 20 carbon atoms]

Examples of the substituent of the alkyl group or the phenyl group include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a cyano group, and the like. Examples of the substituent of the alkanediyl group having 2 to 20 carbon atoms include a hydroxyl group, a cyano group, and a nitro group.

Representative examples of the cation represented by the above formula (9-1) or (9-2) include, for example, cations represented by the following formulas.

The phthalocyanine-based chromophore is preferably represented by the following chemical formula (10).

[In the formula (10)

CuPc represents a copper phthalocyanine residue;

T represents a group represented by the following formula (10a) or (10b)

In the formulas (10a) and (10b)

R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ , R ¹⁵⁶ , R ¹⁵⁷ and R ¹⁵⁸ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group;

p represents, independently of one another, an integer of 2 to 8;

m is the same as the above]

Typical examples of the cations represented by the above formula (10) include, for example, cations represented by the following formulas.

As the xanthan-based chromophore, it is preferably represented by the following chemical formula (11).

In the formula (11)

R ¹⁷¹ , R ¹⁷² , R ¹⁷³ and R ¹⁷⁴ each independently represent a hydrogen atom, -R ¹⁷⁸ or an aromatic hydrocarbon group having 6 to 10 carbon atoms (provided that the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, -R ¹⁷⁸ , -OH, -OR ¹⁷⁸ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ¹⁷⁸ , -SO ₃ R ¹⁷⁸ , -SO ₂ NHR ¹⁷⁹ or -SO ₂ NR ¹⁷⁹ R ¹⁸⁰ Lt; / RTI >

R ¹⁷⁵ and R ¹⁷⁶ independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;

R ¹⁷⁷ represents -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ¹⁷⁸ , -SO ₃ R ¹⁷⁸ , -SO ₂ NHR ¹⁷⁹ or -SO ₂ NR ¹⁷⁹ R ¹⁸⁰ ;

r represents an integer of 0 to 5, and when r is an integer of 2 or more, plural R ¹⁷⁷ may be the same or different;

R ¹⁷⁸ is a saturated hydrocarbon group having 1 to 10 carbon atoms (provided that the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and the methylene group included in the saturated hydrocarbon group may be substituted with an oxygen atom, a carbonyl group, or -NR ¹⁷⁸ - Lt; / RTI >

R ¹⁷⁹ and R ¹⁸⁰ independently represent a linear alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Z, or a substituent having 1 to 10 carbon atoms formed by bonding R ¹⁷⁹ and R ¹⁸⁰ together A hydrogen atom contained in the alkyl group and the cycloalkyl group may be substituted with a hydroxyl group, a halogen atom, -Z, -CH = CH ₂ or -CH = CHR ¹⁷⁸ , and the alkyl group and the cyclo The methylene group contained in the alkyl group may be substituted with an oxygen atom, a carbonyl group or -NR ¹⁷⁸ -, and the hydrogen atom contained in the heterocyclic group may be substituted with -R ¹⁷⁸ , -OH or -Z;

M represents a sodium atom or a potassium atom;

Z represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms, provided that the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is -OH, R ¹⁷⁸ , -OR ¹⁷⁸ , -NO ₂ , -CH = CH ₂ , -CH = CHR ¹⁷⁸ or a halogen atom)

The saturated hydrocarbon group in R ¹⁷⁸ may have any of linear, branched and cyclic, and may have a crosslinked structure when the number of carbon atoms is 1 to 10. Specific examples include a nonyl group, a decanyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecanyl group in addition to the same alkyl group as R ⁴ in the above-mentioned formula (2). Examples of the group in which a methylene group contained in a saturated hydrocarbon group is substituted with an oxygen atom include a methoxypropyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group, and a methoxyhexyl group.

Examples of the substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms formed by bonding R ¹⁷⁹ and R ¹⁸⁰ together include pyrrole, pyridine, indole, isoindole, quinoline, isoquinoline, carbazole, phenanthridine, Furan, pyran, isobenzofuran, isochromene, xanthene, thiophene, thianthrene, phenoxathiine, phenothiazine and the like. Examples of the substituent in the heterocyclic group include a halo group, a hydroxyl group, an alkoxy group, an amino group, and an alkyl group. Examples of the aromatic heterocyclic group having 5 to 10 carbon atoms in Z include a furyl group, a thienyl group, a pyridyl group, a pyrrolyl group, an oxazolyl group, an isoxazole group, a thiazolyl group, an isothiazolyl group, A benzyl group, a benzyl group, a benzyl group, a benzyl group, and a benzyl group.

Examples of the aromatic hydrocarbon group for R ¹⁷¹ , R ¹⁷² , R ¹⁷³ , R ¹⁷⁴ and Z include a phenyl group and a naphthyl group.

Examples of -SO ₃ R ¹⁷⁸ in R ¹⁷¹ , R ¹⁷² , R ¹⁷³ , R ¹⁷⁴ and R ¹⁷⁷ include a methanesulfonyl group, an ethanesulfonyl group, a hexanesulfonyl group and a decanesulfonyl group. Examples of -CO ₂ R ¹⁷⁸ include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a methoxypropyloxycarbonyl group. Examples of R ¹⁷⁹ and R ¹⁸⁰ in -SO ₂ NHR ¹⁷⁹ and -SO ₂ NR ¹⁷⁹ R ¹⁸⁰ include a branched alkyl group having 6 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, an allyl group, An aralkyl group having 1 to 10 carbon atoms, a hydroxyl group-containing alkyl group having 2 to 8 carbon atoms, an alkoxy group-containing alkyl group having 2 to 8 carbon atoms, or an aryl group.

Representative examples of the cation represented by the above formula (11) include, for example, cations represented by the following formulas.

Other cationic chromophores include, for example, cations represented by the following formulas.

This coloring agent can be produced by a known method. For example, the coloring agent can be produced by the same method as in the embodiment of Japanese Patent Application Laid-Open No. 2003-206415. When the present colorant is produced by a salt exchange reaction as in the examples of JP-A-2003-206415, a salt of an anion represented by the above formula (1a-1) is required. As the salt, Or may be synthesized with reference to a known method, for example, referring to the method described in Example 1 of Japanese Patent Laid-Open Publication No. 2011-133844. The present colorant thus obtained is soluble in various organic solvents including ketones such as cyclohexanone, and has excellent heat resistance.

These coloring agents may be used alone or in combination of two or more.

When the coloring agent X ⁺ is a triarylmethane-based coloring agent, for example, when the coloring agent is dissolved in an organic solvent, the coloring agent is blue to red. Therefore, by mixing the coloring agent with the coloring agent alone or by mixing the coloring agent appropriately, A blue pixel, a red pixel, and a colored layer of black.

The coloring composition of the present invention, as a coloring agent, may further contain other coloring agents together with the present coloring agent. The other colorants are not particularly limited, and the color and the material can be appropriately selected depending on the application.

As other coloring agents, pigments other than the present coloring agent, dyes other than the present coloring agent, and natural pigments can be used, and organic pigments and organic dyes are preferable in the sense of obtaining pixels having high luminance and color purity.

As the organic pigment, for example, a compound classified as a pigment in the color index (published by CI., The Society of Dyers and Colourists), that is, a color index (C.I.) name as shown below.

C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 55, C.I., Pigment Yellow 61, C.I. Pigment Yellow 61: 1, C.I. Pigment Yellow 62, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 100, C.I. Pigment Yellow 104, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 133, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 169, C.I. Pigment Yellow 180, C.I. Pigment Yellow 183, C.I. Pigment Yellow 191, C.I. Pigment Yellow 191: 1, C.I. Pigment Yellow 206, C.I. Pigment Yellow 209, C.I. Pigment Yellow 209: 1, C.I. Pigment Yellow 211, C.I. Pigment Yellow 212;

C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 68, C.I. Pigment Orange 70, C.I. Pigment Orange 71, C.I. Pigment Orange 72, C.I. Pigment Orange 73, C.I. Pigment Orange 74;

C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 5, C.I. Pigment Red 17, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 41, C.I. Pigment Red 48: 1, C.I. Pigment Red 48: 2, C.I. Pigment Red 48: 3, C.I. Pigment Red 48: 4, C.I. Pigment Red 48: 5, C.I. Pigment Red 49, C.I. Pigment Red 49: 1, C.I. Pigment Red 49: 2, C.I. Pigment Red 49: 3, C.I. Pigment Red 52: 1, C.I. Pigment Red 52: 2, C.I. Pigment Red 53: 1, C.I. Pigment Red 54, C.I. Pigment Red 57: 1, C.I. Pigment Red 58, C.I. Pigment Red 58: 1, C.I. Pigment Red 58: 2, C.I. Pigment Red 58: 3, C.I. Pigment Red 58: 4, C.I. Pigment Red 60: 1, C.I. Pigment Red 63, C.I. Pigment Red 63: 1, C.I. Pigment Red 63: 2, C.I. Pigment Red 63: 3, C.I. Pigment Red 64: 1, C.I. Pigment Red 68, C.I. Pigment Red 81, C.I. Pigment Red 81: 1, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 200, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 209, C.I. Pigment Red 214, C.I. Pigment Red 220, C.I. Pigment Red 221, C.I. Pigment Red 224, C.I. Pigment Red 237, C.I. Pigment Red 239, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 247, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 262, C.I. Pigment Red 264, C.I. Pigment Red 272;

C.I. Pigment Violet 1, C.I. Pigment Violet 2, C.I. Pigment Violet 3, C.I. Pigment Violet 3: 1, C.I. Pigment Violet 3: 3, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 27, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 38, C.I. Pigment Violet 39; C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3, C.I. Pigment Blue 9, C.I. Pigment Blue 10, C.I. Pigment Blue 14, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 17: 1, C.I. Pigment Blue 24, C.I. Pigment Blue 24: 1, C.I. Pigment Blue 56, C.I. Pigment Blue 60, C.I. Pigment Blue 61, C.I. Pigment Blue 62, C.I. Pigment Blue 80; C.I. Pigment Green 1, C.I. Pigment Green 4, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58; C.I. Pigment Brown 23, C.I. Pigment Brown 25; C.I. Pigment Black 1, C.I. Pigment Black 7.

In the present invention, when a pigment is used as another colorant, the pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. If necessary, the pigment may be used by modifying its particle surface with a resin. Examples of the resin for modifying the particle surface of the pigment include a vehicle resin disclosed in Japanese Patent Laid-Open No. 2001-108817 or a commercially available resin for dispersing various pigments. Examples of the resin coating method for the surface of the carbon black include a method of coating the surface of the carbon black with the resin coating method described in Japanese Patent Application Laid-Open Nos. 9-71733, 9-95625, 9-124969, Method can be adopted. Further, the organic pigment is preferably used by making the primary particles finer by so-called salt milling. As the method of the salt milling, for example, a method disclosed in Japanese Unexamined Patent Application Publication No. 08-179111 can be adopted.

In the present invention, when a pigment is used as the other colorant, known dispersants and dispersion aids may be further contained. Examples of the known dispersing agent include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene alkyl phenyl ether-based dispersant, a polyethylene glycol diester-based dispersant, a sorbitan fatty acid ester- Based dispersing agent, an acrylic-based dispersing agent and the like, and as a dispersing aid, a pigment derivative and the like.

Dispersing agents such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 and BYK-LPN21324 (manufactured by BYK) are commercially available, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170 and Disperbyk-182 (manufactured by BYK), Solpus 76500 (manufactured by Rubriez Co., Ltd.) (Manufactured by Lubrizol Corporation) as a polyethyleneimine-based dispersing agent and the like as a polyester dispersant and Agisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 Manufactured by Techno Corporation), and the like.

Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

Examples of the dyes include various dyes, direct dyes, acid dyes, metal complex dyes and the like, and color index (C.I.) names are given as follows.

C.I. Solvent Yellow 4, C.I. Solvent Yellow 14, C.I. Solvent Yellow 15, C.I. Solvent Yellow 24, C.I. Solvent Yellow 82, C.I. Solvent Yellow 88, C.I. Solvent Yellow 94, C.I. Solvent Yellow 98, C.I. Solvent Yellow 162, C.I. Solvent Yellow 179;

C.I. Solvent Red 45, C.I. Solvent Red 49;

C.I. Solvent Orange 2, C.I. Solvent Orange 7, C.I. Solvent Orange 11, C.I. Solvent Orange 15, C.I. Solvent Orange 26, C.I. Solvent Orange 56;

C.I. Solvent Blue 35, C.I. Solvent Blue 37, C.I. Solvent Blue 59, C.I. Solvent Blue 67;

C.I. Acid Yellow 17, C.I. Acid Yellow 29, C.I. Acid Yellow 40, C.I. Acid Yellow 76;

C.I. Acid Red 91, C.I. Acid Red 92, C.I. Acid Red 97, C.I. Acid Red 114, C.I. Acid Red 138, C.I. Acid Red 151;

C.I. Acid Orange 51, C.I. Acid Orange 63; C.I. Acid Blue 80, C.I. Acid Blue 83, C.I. Acid Blue 90;

C.I. Acid Green 9, C.I. Acid Green 16, C.I. Acid Green 25, C.I. Acid Green 27.

In the present invention, the other colorants may be used alone or in combination of two or more.

In the present invention, when X ⁺ is a methine-based coloring, a coloring composition for forming a green pixel may be used in combination with the present coloring agent and another coloring agent for green, or a coloring composition for forming a red pixel may be used in combination with another coloring agent . In this case, as a green coloring agent as another coloring agent, a green organic pigment is preferable, and at least one kind selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36 and CI Pigment Green 58 is preferable, CI Pigment Green 58 is preferred. As the red coloring agent as another coloring agent, a red organic pigment is preferable, and at least one kind selected from the group consisting of CI Pigment Red 242, CI Pigment Red 254 and CI Pigment Red 264 is preferable.

In the case where X ⁺ is an azo chromophore or quinoneimine based coloring, a coloring composition for forming a blue pixel may be used in combination with the present coloring agent and another coloring agent of blue or a purple coloring agent, or a combination of this coloring agent and another colorant of red To form a colored composition for forming a red pixel. In this case, as the blue coloring agent as another coloring agent, a blue organic pigment is preferable, and CI Pigment Blue 15: 6 is preferable. As a purple coloring agent as another coloring agent, a purple organic pigment is preferable, and CI Pigment Violet 23 is preferable.

When X ⁺ is diarylmethane-based coloring, a coloring composition for forming a green pixel may be used in combination with the present coloring agent and another coloring agent for green, or a coloring composition for forming a red pixel may be used in combination with another coloring agent . In this case, as a green coloring agent as another coloring agent, a green organic pigment is preferable, and at least one kind selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36 and CI Pigment Green 58 is preferable, CI Pigment Green 58 is preferred. As the red coloring agent as another coloring agent, a red organic pigment is preferable, and at least one kind selected from the group consisting of CI Pigment Red 242, CI Pigment Red 254 and CI Pigment Red 264 is preferable.

When X ⁺ is an anthraquinone-based chromophore or a xanthan-based chromophore, it is preferable to use this coloring agent and another coloring agent of blue or another coloring agent of purple color to form a coloring composition for blue pixel formation. In this case, as the blue coloring agent as another coloring agent, a blue organic pigment is preferable, and CI Pigment Blue 15: 6 is preferable. As a purple coloring agent as another coloring agent, a purple organic pigment is preferable, and CI Pigment Violet 23 is preferable.

The content of the coloring agent in this paragraph varies depending on the required chromaticity characteristics, but is usually from 10 to 99% by mass, more preferably from 30 to 95% by mass, still more preferably from 50 to 90% by mass, to be.

The content of the (A) coloring agent is usually from 5 to 70 mass%, preferably from 5 to 60 mass%, more preferably from 5 to 60 mass%, in the solid content of the coloring composition, from the viewpoint of forming a pixel having a high luminance and excellent color purity, to be. The solid content referred to herein is a component other than the solvent described later.

- (B) Binder Resin -

The binder resin (B) in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as a "carboxyl group-containing polymer") is preferable, and for example, an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter also referred to as "unsaturated monomer (b1) (Hereinafter also referred to as "unsaturated monomer (b2)").

Examples of the unsaturated monomer (b1) include unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], omega-carboxypolycaprolactone mono , p-vinylbenzoic acid, and the like.

These unsaturated monomers (b1) may be used alone or in combination of two or more.

As the unsaturated monomer (b2), for example,

N-substituted maleimide such as N-phenylmaleimide, N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene,? -Methylstyrene, p-hydroxystyrene, p-hydroxy-? -Methylstyrene, p-vinylbenzyl glycidyl ether and acenaphthylene;

Acrylates such as methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) (Meth) acrylate, polyethyleneglycol (having a degree of polymerization of 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (having a degree of polymerization of 2 to 10) , Polypropylene glycol (polymerization degree: 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2,1.0 ^2,6 ] decan- Acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of para-cumylphenol, glycidyl (Meth) acrylate, 3,4-di (Meth) acrylate esters such as 3-methyl [(meth) acryloyloxymethyl] -3-ethyloxetane, 3 - [(meth) acryloyloxymethyl] oxetane, 3- ;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) Vinyl ethers such as;

And macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.

These unsaturated monomers (b2) may be used alone or in combination of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition having excellent alkali developability and storage stability can be obtained.

As specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), for example, JP-A-7-140654, JP-A-8-259876, Japanese Patent Application Laid-Open No. H10-31308, Japanese Patent Application Laid-Open No. 10-300922, Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Laid-Open No. 11-258415, -56118, and JP-A-2004-101728, and the like.

Further, in the present invention, for example, Japanese Unexamined Patent Application Publication No. 5-19467, Japanese Unexamined Patent Application Publication No. 6-230212, Japanese Unexamined Patent Application Publication No. 7-207211, (Meth) acryloyl group and the like as a side chain, as disclosed in JP-A-09-325494, JP-A-11-140144 and JP-A-2008-181095 Containing polymer may be used as a binder resin.

The binder resin in the present invention has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, 3,000 to 50,000. If the Mw is too small, the residual film ratio or the like of the resulting film may deteriorate, the pattern shape, heat resistance and the like may be impaired and the electrical characteristics may deteriorate. On the other hand, if the Mw is too large, In addition, there is a concern that dry foreign matter tends to be generated when applying by the slit nozzle method.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. The term "Mn" as used herein refers to the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method. For example, Japanese Unexamined Patent Application Publication No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871 The structure, Mw, and Mw / Mn can also be controlled by the disclosed method.

In the present invention, the binder resins may be used alone or in combination of two or more.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. If the content of the binder resin is too small, for example, the alkali developability may deteriorate or the storage stability of the resulting colored composition may deteriorate. On the other hand, when the content is too large, the concentration of the colorant relatively decreases, There is a possibility that it becomes difficult to achieve the concentration.

- (C) Crosslinking agent -

In the present invention, the (C) crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenic unsaturated group, an oxiranyl group, an oxetanyl group and an N-alkoxymethylamino group. In the present invention, as the crosslinking agent (C), a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, a caprolactone-modified polyfunctional (meth) A polyfunctional urethane (meth) acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, a (meth) acrylate having a hydroxyl group and a And a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting an acid anhydride.

Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; And tri- or higher aliphatic polyhydroxy compounds such as glycerin, trimethylol propane, pentaerythritol and dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Penta (meth) acrylate, and glycerol dimethacrylate. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include acid anhydrides such as anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, anhydrous glutaric acid, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, anhydrous pyromellitic acid, biphenyltetracarboxylic acid Dianhydrides, and tetrabasic acid dianhydrides such as benzophenonetetracarboxylic dianhydrides.

Examples of the caprolactone-modified polyfunctional (meth) acrylate include the compounds described in paragraphs [0015] to [0018] of Japanese Patent Laid-Open No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include di (meth) acrylate modified with at least one selected from an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A, Tri (meth) acrylate modified with at least one member selected from the group consisting of ethylene oxide adducts of dipentaerythritol, ethylene oxide adducts of dipentaerythritol and propylene oxide adduct of isocyanuric acid, ethylene oxide adducts of trimethylolpropane and propylene oxide adducts of trimethylolpropane (Meth) acrylate modified by at least one member selected from the group consisting of tri (meth) acrylate modified with at least one member selected from water, ethylene oxide adducts of pentaerythritol and propylene oxide adducts of pentaerythritol , Ethylene oxide adducts of pentaerythritol and propylene oxide adducts of pentaerythritol Modified with at least one member selected from tetra (meth) acrylate, ethylene oxide adduct of dipentaerythritol and propylene oxide adduct of dipentaerythritol, which is modified by at least one member selected from phenylene oxide adducts (Meth) acrylate modified with at least one member selected from penta (meth) acrylate, ethylene oxide adduct of dipentaerythritol, and propylene oxide adduct of dipentaerythritol, and the like.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. Further, the melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as basic skeletons, and also include melamine, benzoguanamine, or condensates thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N '', N '' - hexa (alkoxymethyl) Tetra (alkoxymethyl) benzoguanamine, N, N, N ', N'-tetra (alkoxymethyl) glycoluril and the like.

Among these crosslinking agents, a polyfunctional (meth) acrylate, a caprolactone modified polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate, and a polyfunctional (meth) acrylate obtained by reacting a trifunctional or higher aliphatic polyhydroxy compound with (meth) (Meth) acrylate having a carboxyl group, N, N, N ', N', N '', N '' - hexa Guanamine is preferred. Among multifunctional (meth) acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, di Among the polyfunctional (meth) acrylates having a carboxyl group, pentaerythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride Compound is particularly preferable in that the strength of the colored layer is high and the surface smoothness of the colored layer is excellent and it is difficult to cause background contamination and film residue on the substrate of the unexposed portion and on the light shielding layer.

In the present invention, the crosslinking agent (C) may be used alone or in combination of two or more.

The content of the crosslinking agent (C) in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. In this case, if the content of the cross-linking agent is too small, there is a fear that sufficient curability can not be obtained. On the other hand, when the content of the crosslinking agent is too large, when the alkali developing property is imparted to the coloring composition of the present invention, the alkaline developing property is lowered, and background contamination or film residue occurs on the substrate of the unexposed portion or on the light- It tends to be easy.

- Photopolymerization initiator -

The coloring composition of the present invention may contain a photopolymerization initiator. Thereby, the coloring composition can be imparted with radiation sensitivity. The photopolymerization initiator used in the present invention is a compound which generates an active species capable of initiating polymerization of the crosslinking agent (C) by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam and X-ray.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, a benzophenone compound , an? -diketone compound, a polynuclear quinone compound, a diazo compound, an imidosulfonate compound, an onium salt compound, and the like.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. As the photopolymerization initiator, at least one member selected from the group consisting of a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, and an O-acyloxime compound is preferable.

Among the preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropyl Thioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone.

Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl- -1- (4-morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- have.

Specific examples of the non-imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2 Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis Phenylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

When a non-imidazole-based compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination because the sensitivity can be improved. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a non-imidazole-based compound by exposure. Examples of the hydrogen donor include a mercaptan-based hydrogen donor such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; And amine hydrogen donors such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. In the present invention, the hydrogen donors may be used singly or in combination of two or more. It is preferable to use one or more kinds of mercaptan-based hydrogen donors and one or more amine-based hydrogen donors in combination to improve the sensitivity .

Specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) ethenyl] -4,6-bis Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) ) -4,6-bis (trichloromethyl) -s-triazine, and other triazine compounds having a halomethyl group.

Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime), ethanone, 1- [ (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime), ethanone, 1- [ -9-ethyl-6- {2-methyl-4- (2, 3-dihydroxy-benzoyl) 2-dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -, 1- (O-acetyloxime). As commercially available products of O-acyloxime compounds, NCI-831 and NCI-930 (manufactured by ADEKA) can be used.

In the present invention, when a photopolymerization initiator other than a non-imidazole-based compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Examples of such sensitizers include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone , Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino- ) Coumarin, and 4- (diethylamino) chalcone.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, per 100 parts by mass of the crosslinking agent (C). In this case, if the content of the photopolymerization initiator is too small, the curing by exposure may become insufficient, while if it is excessively large, the formed colored layer tends to fall off from the substrate at the time of development.

- Solvent -

The coloring composition of the present invention contains the above components (A) to (C), and optionally other components, which are usually prepared as a liquid composition by blending a solvent. The solvent may be appropriately selected and used as long as the components (A) to (C) constituting the coloring composition and other components are dispersed or dissolved, and they do not react with these components and have appropriate volatility have.

Such solvents include, for example,

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, (Poly) alkylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol and cyclohexanol;

Ketoalcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate and 3-methyl- Acid esters;

Amyl acetate, n-butyl acetate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, propyl acetate, isopropyl acetate, n- , N-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Of these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate are preferable from the viewpoints of solubility, pigment dispersibility, Butylene glycol diacetate, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, Diethyl acetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, Amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate are preferable.

In the present invention, the solvents may be used alone or in combination of two or more.

Although the content of the solvent is not particularly limited, the total amount of each component excluding the solvent of the coloring composition is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. By adopting such a form, it is possible to obtain a colorant dispersion having good dispersibility and stability, and a coloring composition having good coatability.

- additive -

The coloring composition of the present invention may contain various additives as required.

As the additive, for example, fillers such as glass and alumina; High molecular compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); Surfactants such as fluorine-based surfactants and silicone-based surfactants; Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like Adhesion promoters; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; An anti-aggregation agent such as sodium polyacrylate; Amino-1-pentanol, 3-amino-1,2-propane, 3-amino-1-pentanol, Diol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like; Developing improvers such as succinic acid mono [2- (meth) acryloyloxyethyl] phthalate mono [2- (meth) acryloyloxyethyl], omega -carboxylic polycaprolactone mono (meth) acrylate; Siloxane oligomers having a reactive functional group disclosed in JP-A-2008-242078, and the like.

The coloring composition of the present invention can be produced by an appropriate method. When the present coloring agent is a dye, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2008-58642, Japanese Patent Application Laid-Open No. 2010-132874 . ≪ / RTI > When both of the present coloring agent and the pigment, which are dyes as a coloring agent, are used, the dye solution containing the present coloring agent or the like is passed through the first filter, as disclosed in Japanese Unexamined Patent Application Publication No. 2010-132874, Mixing the obtained dye solution with a separately prepared pigment dispersion or the like, and passing the obtained coloring composition through a second filter. Further, the dyes containing the present coloring agents and the like, the components (B) to (C), and other components to be used, if necessary, are dissolved in a solvent, the resulting solution is passed through a first filter, Mixing the obtained solution with a separately prepared pigment dispersion, and passing the resulting colored composition through a second filter may be employed. After passing the dye solution containing the present colorant and the like through the first filter, the dye solution which has passed through the first filter, and the components (B) to (C) A method may be employed in which the obtained solution is passed through a second filter and the solution having passed through the second filter is mixed with a separately prepared pigment dispersion and the resulting colored composition is passed through a third filter .

Color filter and manufacturing method thereof

The color filter of the present invention comprises a colored layer containing the present colorant.

As a method of manufacturing the color filter, first, the following method can be mentioned. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to partition a portion where pixels are to be formed, if necessary. Subsequently, the liquid composition of the blue radiation sensitive composition of the present invention containing the coloring agent, for example, is coated on the substrate, followed by prebaking to evaporate the solvent to form a coating film. Subsequently, the coating film is exposed through a photomask, and then developed with an alkali developer to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which blue pixel patterns are arranged in a predetermined arrangement is formed.

Subsequently, the respective radiation-sensitive coloring compositions were applied, pre-baked, exposed, developed, and post-baked in the same manner as above using green or red color sensitive radiation-sensitive compositions to form a green pixel array and a red Pixel arrays are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above. In the first method for manufacturing a color filter, at least one of the blue, green, and red pixel arrays may be a colored layer formed using the coloring composition of the present invention.

The black matrix can be formed by forming a thin metal film of chromium or the like formed by sputtering or vapor deposition into a desired pattern using a photolithography method. By using a radiation-sensitive coloring composition in which a black coloring agent is dispersed, It may be formed in the same manner as in the pixel formation. The coloring composition of the present invention can be suitably used for forming such a black matrix.

Examples of the substrate used for forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.

These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition or the like, if necessary.

When the radiation sensitive coloring composition is applied to a substrate, a suitable coating method such as a spraying method, a roll coating method, a spin coating method, a slit die coating method or a bar coating method can be employed, Method and a slit die coating method are preferably employed.

Prebaking is usually carried out in combination with reduced pressure drying and heat drying. The reduced-pressure drying is usually carried out until 50 to 200 Pa is reached. The conditions for heating and drying are usually about 70 to 110 DEG C for about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8 탆, preferably 1.2 to 5 탆, as a film thickness after drying.

Examples of the light source of radiation used for forming the pixel and / or the black matrix include lamp light sources such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, A laser light source such as an argon ion laser, a YAG laser, an XeCl excimer laser, or a nitrogen laser. An ultraviolet LED may be used as an exposure light source. The wavelength is preferably in the range of 190 to 450 nm.

The exposure dose of the radiation is generally preferably from 10 to 10,000 J / m < ² >.

Examples of the alkali developer include sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] 1,5-diazabicyclo- [4.3.0] -5-nonene and the like are preferable.

A water-soluble organic solvent such as methanol or ethanol, a surfactant or the like may be added to the alkali developing solution in an appropriate amount. After the alkali development, it is usually washed with water.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid immersion) developing method, or the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature.

The post baking condition is usually about 120 to 280 ° C for about 10 to 60 minutes. From the viewpoint of the heat resistance of the present colorant, the post baking temperature is preferably 240 ° C or less, particularly preferably 230 ° C or less.

The film thickness of the thus formed pixel is usually 0.5 to 5 占 퐉, preferably 1 to 3 占 퐉.

As a second method for manufacturing a color filter, there is a method of obtaining pixels of respective colors by the inkjet method disclosed in Japanese Patent Laid-Open Nos. 7-318723 and 2000-310706 Can be adopted. In this method, first, a partition wall serving also as a light shielding function is formed on the surface of the substrate. Subsequently, the liquid composition of the blue thermosetting coloring composition of the invention containing the coloring agent, for example, is discharged by the ink jet apparatus in the partition wall formed, and then the solvent is evaporated by prebaking. Subsequently, this coating film is exposed, if necessary, and then post-baked to form a blue pixel pattern.

Subsequently, a green pixel pattern and a red pixel pattern are successively formed on the same substrate using each of the green or red thermosetting coloring compositions in the same manner as described above. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above. In the second method of manufacturing a color filter, any one of the blue, green, and red pixel arrays may be a colored layer formed using the coloring composition of the present invention.

In addition, the barrier ribs have a thicker film thickness than the black matrix used in the first method, because they function not only to shield the light-shielding function but also to prevent coloring compositions of the respective colors discharged into the compartments from being mixed. Thus, the septum is usually formed using a radiosensitive composition.

The substrate or radiation source used for forming the color filter, and the methods and conditions of pre-baking and post-baking are the same as those of the first method described above. The film thickness of the pixel formed by the ink-jet method in this way is about the same as the height of the partition.

A protective film is formed as necessary on the pixel pattern thus obtained, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to provide a color filter. The spacer is usually formed using a radiation sensitive composition, but it may also be a spacer (black spacer) having light shielding properties. In this case, a radiation-sensitive coloring composition in which a black coloring agent is dispersed is used, and the coloring composition of the present invention can be suitably used for forming such a black spacer.

The color filter of the present invention thus obtained is very useful for a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic EL display element, and an electronic paper because of its extremely high luminance and color purity.

Display element

The display device of the present invention comprises the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and an electronic paper.

The color liquid crystal display element having the color filter of the present invention may be of a transmissive type or a reflective type and may have a suitable structure. For example, the color filter can be formed on a substrate different from the substrate on which the thin film transistor (TFT) is disposed, and the substrate on which the color filter is formed and the substrate for driving can be opposed to each other through the liquid crystal layer. The substrate on which the color filter is formed on the surface of the driving substrate on which the transistor TFT is disposed and the substrate on which the ITO (indium oxide doped indium) electrode is formed may be opposed to each other through the liquid crystal layer. The latter structure can remarkably improve the aperture ratio, and has the advantage that a bright, high-definition liquid crystal display device can be obtained.

The color liquid crystal display device having the color filter of the present invention may have a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). Examples of the white LED include a white LED that combines a red LED with a green LED and a blue LED to obtain white light by mixing colors, a white LED that combines a blue LED, a red LED, and a green phosphor to obtain white light by mixing colors, A white LED which obtains white light by mixing color of a red light emitting phosphor and a green light emitting phosphor, a white LED which obtains white light by mixing of a blue LED and a YAG system phosphor, a blue LED and an orange light emitting phosphor, A white LED for obtaining white light by mixing white light, an ultraviolet LED and a red LED, a white LED for obtaining white light by mixing a green light emitting phosphor and a blue light emitting phosphor in combination, and the like.

The color liquid crystal display device having the color filter of the present invention may be applied to a color liquid crystal display device such as a twisted nematic (TN) type, a super twisted nematic (STN) type, an in-plane switching (IPS) type, a vertical alignment (VA) type, an optically compensated birefringence ) Type liquid crystal mode can be applied.

Further, the organic EL display device having the color filter of the present invention can adopt a suitable structure, for example, a structure disclosed in Japanese Patent Application Laid-Open No. 11-307242.

Further, the electronic paper having the color filter of the present invention can adopt a suitable structure, for example, a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

[Example]

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

≪ Synthesis and evaluation of the present colorant &

1. Synthesis of the present colorant

Synthesis Example 1

Thionyl chloride (12 mmol) was dissolved in DMF (10 mL), and after cooling at 0 캜, 3-sulfopropyl methacrylate (10 mmol) was added in portions. After the reaction for 5 hours, the reaction solution was concentrated, acetone was added to the solution, and the resulting salt was removed by filtration. The filtrate was concentrated to obtain a compound represented by the following formula (A1). The resulting compound is referred to as Intermediate 1.

Synthesis Example 2

Trifluoromethanesulfonamide (20.1 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 30 mL of methylene chloride, and the internal temperature was cooled to 5 占 폚 or lower. Triethylamine (50.4 mmol) manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise so that the internal temperature did not exceed 10 캜. After completion of the dropwise addition, intermediate 1 (20.1 mmol) was added at 10 캜 or lower. After stirring for 1 hour at 5 DEG C or lower, the reaction solution was further stirred at room temperature for 5 hours, and 100 mL of water was added to the reaction solution. The separated organic layer was washed with water, dehydrated with magnesium sulfate, and the organic layer was concentrated under reduced pressure using an evaporator to obtain a compound represented by the following formula (A2). The resulting compound is referred to as intermediate 2.

Synthesis Example 3

A three-necked flask was charged with C.I. BASIC BLUE 7 (2.70 mmol) and 300 mL of water were charged, heated to 80 캜 with stirring, and stirred until dissolved. Then, a solution in which Intermediate 2 (5.40 mmol) was dissolved in 10 mL of water was added and heated at the same temperature for 1 hour. After allowing the reaction solution to cool to room temperature, it was allowed to stand at -15 DEG C for 12 hours. Thereafter, the temperature was returned to room temperature, and the supernatant was removed by decantation. 100 mL of ice water was poured into the residue to wash it. The same operation was repeated three times. The obtained solid was dried under reduced pressure at 60 占 폚 to obtain 450 mg of a dark solid.

^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the obtained compound was a compound represented by the following formula (A3). The resulting compound is referred to as a dye (A-1).

Synthesis Example 4

A compound represented by the following formula (A4) was obtained in the same manner as in Synthesis Example 2, except that methacrylic acid chloride was used instead of the intermediate 1. The resulting compound is referred to as intermediate 3.

Synthesis Example 5

A colorant was synthesized in the same manner as in Synthesis Example 3 except that Intermediate 3 was used instead of Intermediate 2. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the obtained compound was a compound represented by the following formula (A5). The resulting compound is referred to as a dye (A-2).

Synthesis Example 6

In Synthetic Example 3, a colorant was synthesized in the same manner as CI Basic Violet 16, which was a methine based basic dye instead of CI Basic Blue 7. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the target compound was obtained. The resulting compound is referred to as a dye (A-3).

Synthesis Example 7

A colorant was synthesized in the same manner as in Synthesis Example 3 except that CI Basic Red 13, which is a methine-based basic dye, was used in place of CI Basic Blue 7. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the target compound was obtained. The resulting compound is referred to as a dye (A-4).

Synthesis Example 8

In Synthetic Example 3, a colorant was synthesized in the same manner except that CI Basic Yellow 21, which is a methine based basic dye, was used in place of CI Basic Blue 7. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the target compound was obtained. The resulting compound is referred to as a dye (A-5).

Synthesis Example 9

A colorant was synthesized in the same manner as in Synthesis Example 3 except that CI Basic Blue 41, which is an azo basic dye, was used instead of CI Basic Blue 7. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the target compound was obtained. The resulting compound is referred to as a dye (A-6).

Synthesis Example 10

A colorant was synthesized in the same manner as in Synthesis Example 3 except that CI Basic Yellow 25, which is an azo basic dye, was used instead of CI Basic Blue 7. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the target compound was obtained. The resulting compound is referred to as a dye (A-7).

Synthesis Example 11

A colorant was synthesized in the same manner as in Synthesis Example 3 except that CI Basic Orange 24, which is an azo basic dye, was used instead of CI Basic Blue 7. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the target compound was obtained. The resulting compound is referred to as a dye (A-8).

Synthesis Example 12

A colorant was synthesized in the same manner as in Synthesis Example 3, except that CI Basic Blue 2, which is a diarylmethane base basic dye, was used instead of CI Basic Blue 7. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the target compound was obtained. The resulting compound is referred to as a dye (A-9).

Synthesis Example 13

A colorant was synthesized in the same manner as in Synthesis Example 3, except that CI Basic Blue 3, which is a quinone imine basic dye, was used instead of CI Basic Blue 7. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the target compound was obtained. The resulting compound is referred to as a dye (A-10).

Synthesis Example 14

A colorant was synthesized in the same manner as in Synthesis Example 3, except that CI Basic Red 2, which is a quinoneimine basic dye, was used in place of CI Basic Blue 7. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the target compound was obtained. The resulting compound is referred to as a dye (A-11).

Synthesis Example 15

In Synthetic Example 3, a colorant was synthesized in the same manner except that CI Basic Blue 22, which is an anthraquinone basic dye, was used instead of CI Basic Blue 7. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the target compound was obtained. The resulting compound is referred to as a dye (A-12).

Synthesis Example 16

In Synthetic Example 3, a colorant was synthesized in the same manner as CI Basic Violet 11: 1 instead of CI Basic Blue 7, which was a xanthene basic dye. ^It was confirmed by the ¹ H-NMR spectrum (solvent: deuterated chloroform) that the target compound was obtained. The resulting compound is referred to as a dye (A-13).

2. Evaluation of the present colorant

All of the dyes (A-1) to (A-13) obtained in each of the above synthesis examples were dissolved in cyclohexanone in an amount of 10% by mass or more.

Further, the 5% mass reduction temperature based on the simultaneous measurement of the thermogravimetric and differential thermal analysis of the dyes (A-1) to (A-13) was all 250 ° C or more. On the other hand, C.I. Basic Blue 7, C.I. Basic violet 16, C.I. Basic Red 13, C.I. Basic Yellow 21, C.I. Basic Blue 41, C.I. Basic Yellow 25, C.I. Basic orange 24, C.I. Basic Yellow 2, C.I. Basic Blue 3, C.I. Basic Red 2, C.I. Basic Blue 22 and C.I. The 5% mass reduction temperature based on the simultaneous thermogravimetric and differential thermal analysis of Basic Violet 11: 1 was less than 200 ° C. Further, the higher the 5% mass reduction temperature based on the simultaneous thermogravimetric and differential thermal analysis, the higher the heat resistance of the colorant.

≪ Production of Pigment Dispersion >

Production Example 1

As a colorant, C.I. 15 parts by mass of Pigment Violet 23, 12.5 parts by mass (solid content concentration: 40% by mass) of BYK-LPN21116 (BYK) as a dispersant, and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent, To thereby prepare a pigment dispersion (a-1).

≪ Preparation of dye solution >

Production Example 2

15 parts by weight of the dye (A-1) and 85 parts by weight of cyclohexanone were mixed to prepare a dye solution (A-1).

Production Example 3

A dye solution (A-2) was produced in the same manner as in Production Example 2 except that the dye (A-2) was used instead of the dye (A-1) in Production Example 2.

Production Example 4

In Production Example 2, the dye (A-1) was replaced by C.I. A dye solution (A-3) was prepared in the same manner as in Production Example 2, except that Basic Blue 7 was used.

Production Example 5

A dye solution (A-4) was prepared in the same manner as in Production Example 2 except that the dye (A-4) was used instead of the dye (A-1) in Production Example 2.

Production Example 6

A dye solution (A-5) was produced in the same manner as in Production Example 2 except that the dye (A-6) was used instead of the dye (A-1) in Production Example 2.

Production Example 7

A dye solution (A-6) was prepared in the same manner as in Production Example 2, except that the dye (A-11) was used instead of the dye (A-1) in Production Example 2.

Production Example 8

A dye solution (A-7) was prepared in the same manner as in Production Example 2 except that the dye (A-13) was used instead of the dye (A-1) in Production Example 2.

≪ Synthesis of binder resin >

To a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was charged and replaced with nitrogen. The mixture was heated to 80 占 폚 and, at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate , 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 2,2'-azobis (2,4- 6 parts by mass of acrylonitrile) was added dropwise over 1 hour, and the mixture was polymerized at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 占 폚 and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The resulting binder resin had Mw of 12,200 and Mn of 6,500. This binder resin is referred to as "binder resin (B1) ".

≪ Evaluation of voltage holding ratio &

Example 1

7.2 parts by mass of the dye solution (A-1), 9.9 parts by mass of the binder resin (B1) solution as the binder resin, and M-402 (dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate , 1.8 parts by mass of a photopolymerization initiator, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name: IRGACURE 369 available from Ciba Specialty Chemicals Co., , 0.1 part by weight of NCI-930 (manufactured by Adeka Corporation), 0.2 part by weight of Megaface F-554 (manufactured by DIC Corporation) as a fluorine surfactant, and ethyl lactate as a solvent to obtain a colored composition CR1).

The obtained coloring composition (CR1) was spin-coated on a soda glass substrate on which an SiO ₂ film was formed to prevent elution of sodium ions on the surface and an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape, Was prebaked on a hot plate for 1 minute to form a film having a film thickness of 2.0 mu m. Subsequently, the coating film was exposed at an exposure amount of 700 J / m ² without interposing a photomask. Thereafter, this substrate was immersed in a developer containing 0.04 mass% aqueous solution of potassium hydroxide at 23 占 폚 for 1 minute, developed, washed with ultrapure water and air-dried, and post-baked at 230 占 폚 for 30 minutes to cure To form a permanent cured film. Subsequently, the substrate on which the pixel was formed and the substrate on which the ITO electrode had been deposited in a predetermined shape were bonded to each other with a sealant mixed with 1.8 mm glass beads, and then a liquid crystal (MLC6608) made by Merck was injected to manufacture a liquid crystal cell . Subsequently, the liquid crystal cell was placed in a constant temperature layer at 60 占 폚, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage maintaining rate measuring system (VHR-1A type, manufactured by Toyo Technica Co., Ltd.). At this time, the applied voltage was 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is a value obtained by (a voltage applied at a liquid crystal cell potential difference after 16.7 milliseconds / 0 milliseconds). If the voltage holding ratio of the liquid crystal cell is 90% or less, the liquid crystal cell can not keep the applied voltage at a predetermined level for 16.7 milliseconds and can not sufficiently orient the liquid crystal. have. The results are shown in Table 1.

Examples 2 to 6 and Comparative Example 1

Coloring compositions (CR2) to (CR7) were prepared in the same manner as in Example 1 except that the dye solution was changed as shown in Table 1 in Example 1.

Subsequently, a liquid crystal cell was produced in the same manner as in Example 1, and the voltage holding ratio was measured. The results are shown in Table 1.

≪ Evaluation of chromaticity characteristics and contrast &

Example 7

, 13.5 parts by mass of the pigment dispersion (a-1), 7.2 parts by mass of the dye solution (A-1), 9.9 parts by mass of the binder resin (B1) solution as the binder resin, and M-402 (dipentaerythritol 15.4 parts by mass of a mixture of lithol hexaacrylate and dipentaerythritol pentaacrylate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan- , 0.1 part by weight of NCI-930 (manufactured by ADEKA CORPORATION), 0.2 part by weight of Megaface F-554 (manufactured by DIC Corporation) as a fluorinated surfactant, and ethyl lactate as a solvent To prepare a coloring composition (CR8) having a solid content concentration of 20 mass%.

The coloring composition (CR8) was applied on a glass substrate using a spin coater, and then prebaked on a hot plate at 80 DEG C for 10 minutes to form a coating film. By changing the number of revolutions of the spin coater, three coat films having different film thicknesses were formed by the same operation.

Subsequently, these substrates were cooled to room temperature and then irradiated with radiation of each wavelength of 365 nm, 405 nm and 436 nm at an exposure dose of 2,000 J / m ² using a high-pressure mercury lamp without interposing a photomask Exposed. Then, with respect to the substrates, by ejecting 0.04% by mass of 23 ℃ a developer containing an aqueous solution of potassium hydroxide as a developing pressure 1kgf / cm ² (nozzle diameter of 1mm), it was subjected to a shower development for 90 seconds. Thereafter, this substrate was washed with ultrapure water, air-dried, and post-baked in a clean oven at 230 캜 for 30 minutes to form a cured film for evaluation.

Evaluation of chromaticity characteristics

The chromaticity coordinate values (x, y) and the magnetic pole value (Y) in the C light source, the 2-degree field of view, and the CIE colorimetric system were measured using the color analyzer (MCPD2000 manufactured by Otsuka Denshi Co., Ltd.) . Further, the film thickness of the obtained cured film was measured using Alpha Step IQ manufactured by KLA-Tencor. From the measurement results, the chromaticity coordinate value x, the stimulus value Y and the film thickness at the chromaticity coordinate value y = 0.080 were determined. The evaluation results are shown in Table 2. Further, it can be said that the higher the stimulus value (Y), the higher the luminance, and the thinner the film thickness, the greater the coloring power of the colorant.

Contrast  evaluation

The substrate on which the cured film was formed was sandwiched between two polarizing plates and the polarizing plate on the front side was rotated while irradiating with fluorescent light (wavelength range of 380 to 780 nm) from the back side to measure a luminance meter LS-100 (Minolta Co., The maximum value and the minimum value of the light intensity transmitted by the sample were measured. For each of the cured films, a value obtained by dividing the maximum value by the minimum value is referred to as a contrast ratio. From the measurement results, the contrast ratio at the chromaticity coordinate value y = 0.080 was determined. The evaluation results are shown in Table 2.

Example 8, Comparative Example 2

(CR9) to (CR10) were prepared in the same manner as in Example 7 except that the pigment dispersion and the dye solution were changed as shown in Table 2 in Example 7. The obtained coloring compositions (CR9) to (CR10) were evaluated in the same manner as in Example 7. The evaluation results are shown in Table 2.

Claims (10)

(A) a colorant comprising a compound represented by the following formula (1), (B) a binder resin, and (C) a crosslinking agent.

[In the formula (1)
X < ⁺ > represents a cationic chromophore;
Z ^- represents a conjugated base of an organic acid having a polymerizable unsaturated group and a halo group] The coloring composition according to claim 1, wherein Z ^- is an anion represented by the following formula (1a-1).

In the formula (1a-1)
Y ¹ represents a group having a polymerizable unsaturated group;
Y ² represents a halogen group or a halogenated hydrocarbon group which may have a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom] The coloring composition according to claim 2, wherein Y ¹ is a chain organic group having a polymerizable unsaturated group. The coloring composition according to any one of claims 1 to 3, wherein Z ^- is an anion represented by any one of the following formulas (1a-2) and (1a-3).

In the formula (1a-2)
R ¹ represents a (meth) acryloyl group or an allyl group;
X ¹ represents -O- or -O- (R ² O) _q - (*) (wherein R ² represents an alkanediyl group having 2 or 3 carbon atoms, q represents an integer of 1 to 100, *) Represents the bonding hand with X ² );
X ² represents a substituted or unsubstituted alkanediyl group;
Y ² has agreed with the Y ² in the general formula (1a-1)] being

[In the formula (1a-3)
R ³ represents a hydrogen atom or a methyl group;
X ³ represents a single bond or a substituted or unsubstituted alkanediyl group;
Y ² has agreed with the Y ² in the general formula (1a-1)] being 5. The coloring composition according to any one of claims 2 to 4, wherein Y < ² > is a fluoro group, or a fluorinated hydrocarbon group which may have a carbon atom, a hydrogen atom or a linking group containing an atom other than a halogen atom. 6. The coloring composition according to any one of claims 2 to 5, wherein Y < ² > is a group represented by the following formula (1-1) or a group represented by the following formula (1-2).

[In the formula (1-1)
R ²³ represents a hydrogen atom, a fluorine atom, an alkyl group, an alkyl fluoride group, an alicyclic hydrocarbon group, an alkoxy group, an alkoxy fluoride group, R ²⁴ COOR ²⁵ - or R ²⁴ COOR ²⁵ CFH- (R ²⁴ represents an alkyl group, an alicyclic hydrocarbon group, An aryl group, or a substituted or unsubstituted aryl group, and R ²⁵ represents an alkanediyl group;
n represents an integer of 0 or more;
"*" Indicates combined hands)

In the formula (1-2)
R ¹⁸ to R ²² independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkyl fluoride group or an alkoxy group;
"*" Represents a combined hand;
Provided that at least one of R ¹⁸ to R ²² is a fluorine atom or an alkyl fluoride group] 7. The compound according to any one of claims 1 to 6, wherein X ⁺ is a triarylmethane chromophore, a methine chromophore, an azo chromophore, a diarylmethane chromophore, a quinoneimine chromophore, an anthraquinone chromophore, A chromophore or a xanthene chromophore. A color filter comprising a colored layer containing a compound represented by the following formula (1).

[In the formula (1)
X < ⁺ > represents a cationic chromophore;
Z ^- represents an anion represented by the following formula (1a-1)

In the formula (1a-1)
Y ¹ represents a chain organic group having a polymerizable unsaturated group;
Y ² represents a halogen group or a halogenated hydrocarbon group which may have a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom] A display device comprising the color filter of claim 8. A colorant represented by the following formula (1).

[In the formula (1)
X < ⁺ > represents a cationic chromophore;
Z ^- represents an anion represented by the following formula (1a-1)

In the formula (1a-1)
Y ¹ represents a chain organic group having a polymerizable unsaturated group;
Y ² represents a halogen group or a halogenated hydrocarbon group which may have a linking group containing a carbon atom, a hydrogen atom or an atom other than a halogen atom]